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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Radiation-induced transients on solid and molten Li and K iodides

The study, quantification, and monitoring of iodine in nuclear power generation systems have been paramount due to its environmental and health implications. Thorough speciation and transport studies strengthened the development and deployment of water reactors, which are now required for the new generation of Molten Salt Reactors (MSR), where the fuel and coolant are a complex liquid system of suitable halides. The speciation, radiation-induced chemistry, and transport of iodine (I-127, I-129 and I-131) under extreme conditions of temperature and ionizing radiation are among the challenges for the future implementation of MSR’s. In aqueous systems, the triiodide-iodine-iodide (I3--I2-I-) equilibrium is strongly dependent on the conditions of the medium. In molten iodides and chlorides, the triiodide detection (and its disproportionation) poses challenges due to the extreme conditions of temperature and radiation, but studies have shown a dependence on temperature, absorbed dose and salt composition. Through absorption spectroscopy techniques (diffuse reflectance and high-temperature UV-Vis), as well as resonance (Electron Paramagnetic Resonance) it is possible to identify primary transients induced by ionizing radiation trapped in the solid phase (Solid-state radiolysis), and steady-state main absorption components with a fast-acquisition real-time spectroscopy. The presence of heterogeneous phase (colloids), viscosity changes, and gas evolution are among the observed processes. A specific case of study is speciation in the presence of Ni. A corrosion product with magnetic properties due to unpaired electrons in its electronic structure. Ferromagnetic materials are monitored in solidified salts to identify aggregation and phase separation. Comparative studies of eutectic mixtures of LiI-KI and LiCl-KCl with known addition of dopants will be presented, with a perspective of radiation chemistry and its possible implications in complex systems.

36 - MATERIALS SCIENCE↗
DOE OSTI2025

Multi-phase characterization of pitch-carbon coated nano-silicon anodes for lithium-ion batteries

Silicon (Si) is a leading next-generation Li-ion battery anode candidate that meets rigorous performance demands for portable power including enhanced power and energy density with robust cycling performance. However, a series of complex and interrelated reactions lead to reduced calendar life in Si-containing systems and therefore challenge practical adoption. In the present work, we probe the mechanisms underlying observed performance improvements by adding a pitch-carbon coating onto nano-Si material. We pair solid-phase (X-ray photoemission spectroscopy, Fourier-transform infrared), semi-volatile phase (solid-phase microextraction-gas chromatography-mass spectrometry), and gas-phase (gas chromatography-flame-ionization detector) characterization signals to comprehensively evaluate the impact of pitch-carbon coating on the evolution of the Si solid-electrolyte interphase (SEI) and the associated impacts on electrode/electrolyte reactivity. The pitch-carbon is found to serve as a physicochemical barrier, reducing the electro-active surface area for Si/electrolyte reactivity and preventing Si oxidation. Further, the pitch-carbon coating promotes the evolution of a more-favorable SEI by subsuming substantial functionality typically associated with the fluoroethylene carbonate (FEC) electrolyte additive - such as alkoxide scavenging and suppression of transesterification pathways - and by shifting the competitive electrolyte degradation pathways' favorability. The multi-phase characterization approach enables holistic end-products evaluation from complex (electro)chemical interfacial reactions, which informs a robust interpretation of the carbon coating's role in electrochemical performance improvements. The present mechanistic evaluation aids the rational design for improved nano-Si materials.

25 ENERGY STORAGE↗
DOE OSTI2016

Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Impact of alloy composition on one-dimensional glide of small dislocation loops in concentrated solid solution alloys

One-dimensional glide of loops during ion irradiation at 773 K in a series of Ni-containing concentrated solid solution alloys has been observed directly during experiments conducted inside a transmission electron microscope. It was found that the frequency of the oscillatory motion of the loop, the loop glide velocity as well as the loop jump distance were dependent on the composition of the alloy and the size of the loop. Loop glide was most common for small loops and occurred more frequently in the less complex alloys, being highest in Ni, then NiCo, NiFe and NiCoFeCr. As a result, no measurable loop glide occurred in the NiCoCr, NiCoFeCrMn and NiCoFeCrPd alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Solid Electrolyte Bimodal Grain Structures for Improved Cycling Performance

Here, the application of solid-state electrolytes in Li batteries is hampered by the occurrence of Li-dendrite-caused short circuits. To avoid cell failure, the electrolytes can only be stressed with rather low current densities, severely restricting their performance. As grain size and pore distributions significantly affect dendrite growth in ceramic electrolytes such as Li 7 La 3 Zr 2 O 12 and its variants; here, a “detour and buffer” strategy to bring the superiority of both coarse and fine grains into play, is proposed. To validate the mechanism, a coarse/fine bimodal grain microstructure is obtained by seeding unpulverized large particles in the green body. The rearrangement of coarse grains and fine pores is fine-tuned by changing the ratio of pulverized and unpulverized powders. The optimized bimodal microstructure, obtained when the two powders are equally mixed, allows, without extra interface decoration, cycling for over 2000 h as the current density is increased from 1.0 mA·cm -2 , and gradually, up to 2.0 mA·cm -2 . The “detour and buffer” effects are confirmed from postmortem analysis. The complex grain boundaries formed by fine grains discourage the direct infiltration of Li. Simultaneously, the coarse grains further increase the tortuosity of the Li path. This study sheds light on the microstructure optimization for the polycrystalline solid-state electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2019

Interplay between Composition, Electronic Structure, Disorder, and Doping due to Dual Sublattice Mixing in Nonequilibrium Synthesis of ZnSnN 2 :O

We report the opportunity for enhanced functional properties in semiconductor solid solutions has attracted vast scientific interest for a variety of novel applications. However, the functional versatility originating from the additional degrees of freedom due to atomic composition and ordering comes along with new challenges in characterization and modeling. Developing predictive synthesis-structure-property relationships is prerequisite for effective materials design strategies. Here, a first-principles based model for property prediction in such complex semiconductor materials is presented. This framework incorporates nonequilibrium synthesis, dopants and defects, and the change of the electronic structure with composition and short range order. This approach is applied to ZnSnN 2 (ZTN) which has attracted recent interest for photovoltaics. The unintentional oxygen incorporation and its correlation with the cation stoichiometry leads to the formation of a solid solution with dual sublattice mixing. A nonmonotonic doping behavior as a function of the composition is uncovered. Finally, the degenerate doping of near-stoichiometric ZTN, which is detrimental for potential applications, can be lowered into the 10 17 cm -3 range in highly off-stoichiometric material, in quantitative agreement with experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Conception and Operation of a New Treatment Center for Radioactive Waste from High Energy Accelerators - 18293

CERN has operated high-energy accelerators for more than 60 years of research in fundamental physics. The side-product of this activity is the generation of low- and intermediate-level radioactive waste, most of which is in solid form and free of surface contamination. Today, one operational year produces about 400 tons of radioactive waste which need to be disposed of towards the final repositories of the two CERN Host States, France and Switzerland. A new facility for the collection, interim storage, characterization and treatment of radioactive waste became operational at CERN in 2015. This facility was specifically conceived for an accelerator complex with a wide range of challenging waste items, which are often unique in their irradiation history as well as in their physical, chemical and radiological characteristics. The disposal rate was ramped up in 2016 with a unique treatment process tailored for metallic low-level waste. In 2017, two parallel processes were successfully tested for the elimination of radioactive cables and for the recycling of valuable metals. This paper gives an overview of the challenges in the design, commissioning and operation of the CERN radioactive waste treatment center. It outlines the methodology followed for the conception of the elimination processes, which can be of guidance for the development of similar facilities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Nanoscale building blocks in a novel lithium arsenotungsten bronze: Synthesis and characterization

We report on a novel compound Li{sub 3}AsW{sub 7}O{sub 25} obtained by solid-state reaction and characterized by diffraction and spectroscopic methods. The bronze-type compound crystallizes in the orthorhombic space group Pbca with a=724.38(3) pm, b=1008.15(4) pm, c=4906.16(17) pm and Z=8. The structure is built up by chains of WO{sub 6} octahedra interconnected by AsO{sub 4} tetrahedra and WO{sub 6} octahedra forming a polyhedral arrangement as seen in intergrowth tungsten bronzes. The X-ray single crystal structure refinement allows solving the complex arsenotungstate framework. The powder neutron diffraction data analysis locates the lithium atoms. Thermal analysis showed that Li{sub 3}AsW{sub 7}O{sub 25} is stable up to its melting at 1135(3) K followed by a decomposition at 1182(5) K. The Kubelka–Munk treatment of the UV–vis spectrum revealed a wide band gap in the range of 2.84–3.40 eV depending on the presumed electron transition type. - Graphical abstract: Crystal structure of Li{sub 3}AsW{sub 7}O{sub 25} showing different schematic components. - Highlights: • A report on a novel compound Li{sub 3}AsW{sub 7}O{sub 25} obtained by solid-state reaction. • Chains and nano-blocks of WO{sub 6} octahedra and AsO{sub 4} tetrahedra formed a structure like intergrowth tungsten bronzes. • X-ray diffraction allowed solving the complex arsenotungstate framework. • Powder neutron diffraction data analysis locates the lithium atoms. • UV–vis spectrum revealed the band-gap.

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

Update on Full-Scale Retrieval and Transfer System Testing for Pneumatic Conveyance of High-Level Calcine Waste - 20241

The Idaho National Laboratory processed spent nuclear fuel from 1953 to 1994. The process used solvent extraction to separate uranium, resulting in a liquid waste. A calcination process was used to convert the liquid waste to a high-level radioactive solid powder, referred to as calcine. The calcine is stored in stainless steel bins contained within concrete vaults called the Calcined Solids Storage Facilities. There are a total of seven CSSFs. The Calcine Retrieval Project is tasked with retrieving the calcine from the bins of CSSF 1 and pneumatically transferring it to the bins of CSSF 6. CSSF 1 was constructed to be a final calcine repository with no forethought of retrieval. It represents the greatest technical hurdle to calcine extraction of all the CSSFs. The challenges inherent with accessing the calcine, safely extracting it, and securely transporting it are copious and complex. Once the calcine is removed from CSSF1, that facility may be closed, reducing the footprint of waste storage at the INL. The same process for removing Calcine from CSSF1 may then be utilized to remove the calcine from the remaining CSSFs for final treatment and transport to a long-term storage facility. To overcome these inherent challenges with accessing CSSF 1 and extracting the calcine in a timely manner, a full-scale integrated mockup has been constructed. The mockup includes a full-size model of a concentric group of bins from CSSF 1 and a storage vessel representing CSSF 6. All essential elements of the transport design are represented in the Mockup, including motive and makeup air supply (air compressor), a replica of the CSSF6 cyclone, pre-filter, HEPA filter, vacuum pump, and retrieval control devices. Construction on the Mockup was completed in 2018 and testing began in February 2019. It has already proven very beneficial to the CRP. Experience in running the Mockup have aided in the development of retrieval and transport methodologies and the selection of process parameter values. It has also uncovered some unforeseen technological challenges and will continue to be valuable to the testing team as these hurdles are overcome and the process is proven effective. Operations personnel have also benefitted from its use as a training tool and will continue to use the Mockup as a simulator to reproduce problems encountered during extraction and transfer of Calcine from CSSF 1. The knowledge gained during this process will also be of continued benefit as future work is done to remove various types of calcine from the remaining CSSFs. The methodology of safe and secure transfer of radioactive material may be of benefit to others throughout the U.S. Department of Energy complex. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Phase equilibria and crystal structure of the complex oxides in the Ln-Ba-Co-O (Ln=Nd, Sm) systems

The phase equilibria in the Ln-Ba-Co-O (Ln=Nd, Sm) systems were systematically studied at 1100 deg. C in air. The homogeneity ranges and crystal structure of the solid solutions: Ln{sub 2-x}Ba{sub x}O{sub 3-{delta}} (0<x{<=}0.1 for Ln=Nd and 0<x{<=}0.3 for Ln=Sm), Nd{sub 3-y}Ba{sub y}Co{sub 2}O{sub 7} (0.70{<=}y{<=}0.80), BaCo{sub 1-z}Sm{sub z}O{sub 3-{delta}} (0.1{<=}z{<=}0.2) were determined by X-ray diffraction of quenched samples. The values of oxygen content (5+{delta}) for slowly cooled LnBaCo{sub 2}O{sub 5+{delta}} (Ln=Nd, Sm) samples were estimated as 5.73 for Ln=Nd, and 5.60 for Ln=Sm. The unit cell parameters were refined using Rietveld full-profile analysis. It was shown that NdBaCo{sub 2}O{sub 5.73} possesses tetragonal structure and SmBaCo{sub 2}O{sub 5.60} - orthorhombic structure. The projections of isothermal-isobaric phase diagrams for the Ln-Ba-Co-O (Ln=Nd, Sm) systems to the compositional triangle of metallic components were presented. - Graphical Abstract: Projections of isobaric isothermal phase diagrams of the Nd-Ba-Co-O system and Sm-Ba-Co-O system. Highlights: > Phase equilibria in the Ln-Ba-Co-O systems (Ln=Nd, Sm). > The homogeneity range for Nd{sub 2-x}Ba{sub x}O{sub 3-{delta}} solid solutions at studied conditions 0<x{<=}0.1. > The homogeneity range for Sm{sub 2-x}Ba{sub x}O{sub 3-{delta}} solid solutions at studied conditions 0<x{<=}0.3. > Nd{sub 3-y}Ba{sub y}Co{sub 2}O{sub 7} solid solutions within the range 0.7{<=}y{<=}0.8. > BaCo{sub 1-z}Sm{sub z}O{sub 3-{delta}} solid solutions within the range 0.1{<=}z{<=}0.2.

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

On the Effects of Aliovalent Substitutions in Thermoelectric Zintl Pnictides. Varied Polyanionic Dimensionality and Complex Structural Transformations–The Case of Sr 3 ZnP 3 vs Sr 3 Al x Zn 1– x P 3

The structures and the transport properties of a novel family of Zintl phosphides and arsenides with the formula AE 3 ZnPn 3 and the solid solutions AE 3 Al x Zn 1–x Pn 3 , AE 3 ZnAs y P 1–y (AE = Sr, Eu; Pn = P, As) are reported. Crystals of nine new phases have been obtained via Pb-flux reactions and used for structural work by means of single-crystal X-ray diffraction methods. The derived orthorhombic structure is without a direct analog, and features unusual structural units, where the Zn atoms are in both distorted tetrahedral and trigonal-planar coordination of pnictogens. Electronic structure calculations reveal moderately wide bandgaps for Sr 3 ZnP 3 and Sr 3 ZnAs 3 , on the order of 0.70 and 0.63 eV, respectively. Electrical transport measurements above room temperature indicate relatively high resistivity values above 500 K (ρ ≈ 4.8 Ω cm and above), but some of the samples exhibit very high Seebeck coefficients, as large as 300 μV/K at 560 K for Sr 3 ZnAs 3 . Aliovalent substitutions in AE 3 ZnPn 3 , achieved by the partial replacement of Zn 2+ with Al 3+ cations promote occupational and positional disorder, which causes structural transformation towards the disordered variant of the Sr 5 Al 2 Sb 6 structure type. Such substitutions also change the dimensionality of the polyanionic sub-lattice in the resulting quaternary AE 3 Al x Zn 1–x Pn 3 phases. Furthermore, preliminary transport property data on the latter reveal nine times lower electrical resistivity (ρ 500 ≈ 0.5 Ω cm) together with a significantly enhanced Seebeck coefficient, αmax ≈ 430 μV/K at 560 K.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The role of surface forces in environment-enhanced cracking of brittle solids

Fracture initiation and propagation in brittle materials is promoted in surface-reactive (sorptive) environments, a phenomenon known as subcritical crack growth (SCG). Laboratory measured crack-propagation velocity vs. stress intensity factor relationships typically exhibit highly nonlinear, multi-stage characteristics that are sensitive to environmental factors such as adsorbate concentration and temperature. For practical purposes, empirical relationships (e.g., a power law) have been used to describe this complex phenomenon. However, how the overall SCG behavior emerges from the underlying fundamental processes near the crack tip, such as the interaction of the crack surfaces separated by only a few nanometers and mass transport within the nano-confined space, is still not well understood. This paper develops a mechanistic, surface-force-based fracture theory (SFFT) which integrates surface force models, fluid transport models, and linear elastic fracture mechanics to quantitatively explain the multi-stage characteristics of SCG in brittle solids. A numerical model is developed based on SFFT and solved through an implicit partitioned scheme for efficiency and modularity. The results are validated by Wiederhorn's data on crack propagation in soda-lime glasses at a wide range of relative humidity levels. We show that, for the first time, the entire range of an SCG curve can be captured by a single physics-based model. The predicted SCG curves reveal that the development of repulsive disjoining pressure behind the crack tip can be responsible for the reduced apparent fracture toughness in a sorptive environment. In conclusion, the shape of the SCG curve, and its changes with respect to the environment, is found to critically depend on the assumed transport models.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Beyond Charge Balance: Counter-Cations in Polyoxometalate Chemistry

Polyoxometalates (POMs) are molecular metal-oxide anions applied in energy conversion and storage, manipulation of biomolecules, catalysis, as well as materials design and assembly. Although often overlooked, the interplay of intrinsically anionic POMs with organic and inorganic cations is crucial to control POM self-assembly, stabilization, solubility, and function. Beyond simple alkali metals and ammonium, chemically diverse cations including dendrimers, polyvalent metals, metal complexes, amphiphiles, and alkaloids allow tailoring properties for known applications, and those yet to be discovered. This review provides an overview of fundamental POM– cation interactions in solution, the resulting solid-state compounds, and behavior and properties that emerge from these POM–cation interactions. We will explore how application-inspired research has exploited cation-controlled design to discover new POM materials, which in turn has led to the quest for fundamental understanding of POM–cation interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Linking two worlds in polymer chemistry: The influence of block uniformity and dispersity in amphiphilic block copolypeptoids on their self‐assembly

Abstract The self‐assembly of block copolymers has captured the interest of scientists for many decades because it can induce ordered structures and help to imitate complex structures found in nature. In contrast to proteins, nature's most functional hierarchical structures, conventional polymers are disperse in their length distribution. Here, we synthesized hydrophilic and hydrophobic polypeptoids via solid‐phase synthesis (uniform) and ring‐opening polymerization (disperse). Differential scanning calorimetry measurements showed that the uniform hydrophobic peptoids converge to a maximum of the melting temperature at a much lower chain length than their disperse analogs, showing that not only the chain length but also the dispersity has a considerable impact on the thermal properties of those homopolymers. These homopolymers were then coupled to yield amphiphilic block copolypeptoids. SAXS and AFM measurements confirm that the dispersity plays a major role in microphase separation of these macromolecules, and it appears that uniform hydrophobic blocks form more ordered structures.

Gangloff, Niklas↗
DOE OSTI2019

Real time imaging of two-dimensional iron oxide spherulite nanostructure formation

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. Finally, a growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Current interrupt method for calculating the electrochemical impedance in a solid oxide electrolysis stack

Here, in this work the time domain response of Solid Oxide Electrolysis Cells (SOEC) to a current interruption was transformed into the frequency domain using a carrier function Laplace transform, which is fit to the experimental data using a MATLAB Complex Nonlinear Least Squares (CNLS) solver. The hardware implementation, consisting principally of a high-speed switch and a fast-logging Analog to Digital Converter (ADC), was assembled and tested using a calibration module to assess the accuracy, repeatability, and speed of acquisition of the prototype device as compared against a calibrated commercial impedance spectrometer. Additionally, the current interrupt device and commercial FRA were used to acquire the impedance spectra of a four cell SOEC stack with a large, 300 cm 2 , active cell area.

SOEC↗
DOE OSTI2025

Homoleptic An(IV) Dimethyl Sulfoxide Complexes of Th–Pu Enable Insight into Solution Speciation and Redox

A family of 8- and 9- coordinate homoleptic dimethyl sulfoxide An(IV) complexes is used to evaluate the solvation properties of tetravalent actinide ions in dimethyl sulfoxide (DMSO) vs aqueous media. These compounds are prepared from aqueous mixtures of DMSO and yield crystalline solids, whose solid-state electronic absorption spectra are compared to solution phase spectra, providing insight into the solution speciation. The thermodynamics of the equilibria between the 8- and 9-coordinate compounds were determined experimentally and computationally, showing a trend that correlates with ionic radius. Cyclic voltammetry data for the +IV/+III couples of Np and Pu in the DMSO electrolyte indicate that the +IV ions are significantly stabilized compared to aqueous media due to the more donating nature of DMSO compared to water. As a result, computational studies of these systems indicate that further reactivity may take place upon reduction to the +III oxidation state.

Actinides↗
DOE OSTI2023

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗