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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 1,765 records · Page 98

Tuning domain size and crystallinity in isoindigo/PCBM organic solar cells via solution shearing

Despite having achieved the long sought-after performance of 10% power conversion efficiency, high performance organic photovoltaics (OPVs) are still mostly constrained to lab scale devices fabricated by spin coating. Efforts to produce printed OPVs lag considerably behind, and the sensitivity to different fabrication methods highlights the need to develop a comprehensive understanding of the processing-morphology relationship in printing methods. Here we present a systematic experimental investigation of a model low bandgap polymer/fullerene system, poly-isoindigo thienothiophene/PC 61 BM, using a lab-scale analogue to roll-to-roll coating as the fabrication tool in order to understand the impact of processing parameters on morphological evolution. We report that domain size and polymer crystallinity can be tuned by a factor of two by controlling the temperature and coating speed. Lower fabrication temperature simultaneously decreased the phase separation domain size and increased the relative degree of crystallinity in those domains, leading to improved photocurrent. We conclude that domain size in isoindigo/PCBM is dictated by spontaneous phase separation rather than crystal nucleation and growth. Moreover we present a model to describe the temperature dependence of domain size formation in our system, which demonstrates that morphology is not necessarily strictly dependent on the evaporation rate, but rather on the interplay between evaporation and diffusion during the printing process.

14 SOLAR ENERGY↗

Electrical injection and transport in Teflon-diluted hole transport materials

Diluting small molecule organic semiconductor hole transport materials with Teflon AF (TAF) dramatically increases their thermal/morphological stability while counterintuitively also increasing the current density in hole-only diodes. Here, we explore the origin of this current enhancement in co-evaporated blends of TAF and N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD) and find that it results from improved hole injection and not from a mobility enhancement due to semiconductor dilution effects. Whereas electroabsorption measurements indicate that an interface dipole shift of up to 0.5 eV (depending on TAF concentration) aides hole injection at the indium-tin-oxide anode, time-of-flight and temperature-dependent current-voltage measurements show that the mobility of 25 vol% TAF:NPD blends decreases by roughly an order of magnitude relative to neat NPD despite having slightly lower energetic disorder. For comparison, diluting with 25 vol% high density polyethylene achieves a similar reduction in energetic disorder but only decreases the mobility by a factor of two. Furthermore, these results highlight the tradeoff between reducing energetic disorder and frustrating percolation in diluted organic semiconductors, and represent a step toward thermally-evaporated polymer-small molecule composites that maintain high mobility while offering improved morphological stability and lower refractive index for organic light emitting diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A mathematical design framework for membrane pre-concentration in energy-efficient recovery of fermentation products

Due to the dilute nature of products manufactured via fermentation and cell-free bioprocessing, dewatering is a common unit operation in downstream processing (DSP) for bioproduct recovery, but it is typically energy intensive. To improve DSP energy efficiency for bio-based small molecules, integrating high-pressure membrane pre-concentration is a promising process option. However, this approach is typically constrained by a tradeoff between concentration factor (CF) and product recovery (PR), namely increasing the CF typically results in greater product loss, and vice versa. Here we developed a model that enables process design guidelines to: (i) identify scenarios in which the additional energy consumption and product loss from membrane pre-concentration are justified for use in DSP, and (ii) determine the optimal CF that minimizes process specific energy consumption. We compared the energy consumption of high-pressure membrane-integrated processes to evaporation-only processes and applied the model to an experimental case study for the separation and purification of butyric acid from Clostridium tyrobutyricum fermentation using an in situ product recovery (ISPR) process. The model estimated that integrating a tangential-flow reverse osmosis (RO) pre-concentration unit could reduce process energy consumption up to 45%. The use of advanced membrane pre-concentration technologies, such as negative rejection membranes and organic solvent reverse osmosis (OSRO), have the potential to further reduce the overall process specific energy consumption up to 96%, projected based on modeling. Overall, membrane pre-concentration, especially when strategically integrated prior to an evaporation step with optimized process conditions, holds significant potential for improving DSP energy efficiency, particularly in applications requiring substantial solvent removal for product recovery from dilute mixtures.

09 BIOMASS FUELS↗

Innovative high-temperature ammonium bifluoride fusion and rapid analysis of elements with nuclear forensic value

High-temperature ammonium bifluoride (ABF) fusions were evaluated for potential use in rapid dissolution of post-detonation nuclear debris. The ABF fusion was carried out in a Pt crucible which allowed evaluation of higher fusion and evaporation temperatures. The high-temperature ABF fusion dissolution method was evaluated using geological reference materials: USGS QLO-1a Quartz Latite, USGS SDC-1 Mica Schist, and NIST 278 Obsidian Rock. The optimized dissolution method involved a 10 min fusion at 540 °C, a 5 min reflux in 8 M HNO 3 , an evaporation at 300 °C and final dilution into 45 mL of 2% (v/v) HNO3. The final solution was filtered after heating at 105 °C using a hotblock. This dissolution method was simple, requiring only a hotplate or hotblock, filtered samples were available for ICP-MS analysis or radiochemical separation within 150 min, and was found to have high (>90%) recovery for many isotopes of interest in nuclear forensics applications. U and Pu in the dissolved material was separated using TEVA and UTEVA extraction chromatography columns, a process which resulted in >90% recovery. An irradiated U tracer was spiked into the material prior to dissolution and analyzed for recovery of major fission products and 239Np. The monitored radionuclides had recoveries of greater than 90%, except for the volatile radioiodine isotopes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation and optimization of flow boiling frictional pressure drop correlations using the data from traditional and next-generation refrigerants in a micro-fin tube

This study presents an experimental evaluation and optimization of flow boiling frictional pressure drop correlations for conventional and next-generation refrigerants in a horizontal micro-fin tube, with particular emphasis on the newly emerging refrigerant blends R-454C and R-455A, for which pressure-drop data in enhanced tubes remain limited. Experiments were conducted with R-410A, R-454C, R-455A, R-134a, R-1234yf, and R-1234ze(E) in a copper micro-fin tube with an inner diameter of 8.468 mm, over mass fluxes ranging from 100 to 300 kg/(m²·s) depending on the refrigerant, and evaporation temperatures of 7, 12, and 14 °C. Frictional pressure gradients were determined from measured total pressure drops after subtracting acceleration pressure drop, and the resulting database was used to assess four existing models: Kuo and Wang (1996), Cavallini et al. (1997), Goto et al. (2001), and Diani et al. (2014). The measured frictional pressure gradient increased with vapor quality and mass flux for all refrigerants and increased further at lower evaporation temperatures, with the overall trend strongly related to liquid viscosity. Among the four correlations, the Goto et al. (2001) model provided the best overall agreement with the measured data before optimization. To further improve prediction accuracy, the Kuo and Wang (1996) and Goto et al. (2001) models were optimized using the complete experimental database. After optimization, both models reduced the overall mean absolute deviation to below 15%, while the optimized Goto et al. (2001) model maintained the best and most consistent overall performance. The results provide new pressure-drop data for next-generation refrigerants and demonstrate that parameter optimization can significantly enhance the applicability of existing micro-fin-tube correlations.

Hu, Yifeng [ORNL] (ORCID:0000000242875185)↗

Describing the Influence of Ball-milling on the Amorphization of Flubendazole Using the PDF and RMC Methods with X-ray Powder Diffraction Data

Flubendazole (FBZ) is a poorly water-soluble drug, and different methodologies have been proposed to improve its oral bioavailability. Obtaining the amorphous drug phase is an alternative to improve its water solubility. Several techniques for drug amorphization, such as spray drying, lyophilization, melt quenching, solvent-evaporation, and ball milling, can yield various types of structural disorder and possibly render variations in physicochemical properties. Herein, we focus on evaluating the influence of the ball-milling process on the amorphization of FBZ. The characterization of the average global and local structures before, during, and after the milling process is described by sequential Rietveld refinements, pair distribution function analysis, and the Reverse Monte Carlo method. In conclusion, we show that preserving the local structure (nearest molecules) can be responsible for avoiding the fast structure recrystallization commonly observed when using the solvent-evaporation process for the studied drug.

60 APPLIED LIFE SCIENCES↗

Orientational Order in Spin-Cast Lead-Iodide Perovskite Nanocrystal Solids

Combined synthetic control over size and composition renders colloidal lead-halide perovskite nanocrystals a tunable platform for high-efficiency optoelectronic applications. However, the properties and operational stability of devices based on nanocrystal solids are often dictated by the method of the evaporation-induced assembly. Ubiquitous slow evaporation techniques can produce highly ordered nanocrystal domains but limit the prospects for scalable fabrication of continuous device layers, calling for investigation of approaches to more rapidly form ordered perovskite nanocrystal solids. Here, we study orientationally ordered lead-iodide perovskite nanocrystal solids prepared by conventional spin coating with molecular additives (excess ligand) to enhance ordering within the arrays. In situ X-ray scattering measurements reveal that orientational ordering occurs rapidly upon solvent removal during spin coating and can be further enhanced by manipulating the spin speed. We vary the additive ligand length and explore trade-offs between ordering and layered perovskite impurity formation. Arrays treated with the intermediate-length octylamine ligand exhibit increased in-plane electronic conductivity, suggesting orientational ordering and internanocrystal electronic coupling can be enhanced by the treatment. In conclusion, these results highlight the prospects of establishing long-range order in lead-halide perovskite nanocrystal solids by using simple and fast coating methods.

14 SOLAR ENERGY↗

A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides

Despite the significant progress in fabricating hybrid organic-inorganic lead halide perovskite solar cells, their toxicity and low stability remain as major drawbacks, thereby hindering large-scale commercialization. Given the isoelectronic nature of lead(II) and bismuth(III) ions, potentially stable and non-toxic alternatives for efficient light absorption in thin-film photovoltaic (PV) devices may be found among bismuth-based halide semiconductors. However, high-quality polycrystalline films of many of these systems have not been demonstrated. In this work, we present a versatile and facile two-step co-evaporation approach to fabricate A 3 Bi 2 I 9 (A = Cs, Rb) and AgBi 2 I 7 polycrystalline films with smooth, pin-hole-free morphology and average grain size of > 200 nm. The process involves an initial two-source evaporation step (involving CsI, RbI or AgI, and BiI 3 sources), followed by an annealing step under BiI3 vapor. The structural, optical and electrical characteristics of the resulting thin films are studied by X-ray diffraction, optical spectroscopy, X-ray/UV photoelectron spectroscopy and scanning electron microscopy.

36 MATERIALS SCIENCE↗

Floating Photovoltaic Systems: Assessing the Technical Potential of Photovoltaic Systems on Man-Made Water Bodies in the Continental United States

We report that floating photovoltaic (FPV) systems, also called floatovoltaics, are a rapidly growing emerging technology application in which solar photovoltaic (PV) systems are sited directly on water. The water-based configuration of FPV systems can be mutually beneficial: Along with providing such benefits as reduced evaporation and algae growth, it can lower PV operating temperatures and potentially reduce the costs of solar energy generation. Although there is growing interest in FPV, to date there has been no systematic assessment of technical potential in the continental United States. We provide the first national-level estimate of FPV technical potential using a combination of filtered, large-scale datasets, site-specific PV generation models, and geospatial analytical tools. We quantify FPV co-benefits and siting considerations, such as land conservation, coincidence with high electricity prices, and evaporation rates. Our results demonstrate the potential of FPV to contribute significantly to the U.S. electric sector, even using conservative assumptions. A total of 24?419 man-made water bodies, representing 27% of the number and 12% of the area of man-made water bodies in the contiguous United States, were identified as being suitable for FPV generation. FPV systems covering just 27% of the identified suitable water bodies could produce almost 10% of current national generation. Lastly, many of these eligible bodies of water are in water-stressed areas with high land acquisition costs and high electricity prices, suggesting multiple benefits of FPV technologies.

14 SOLAR ENERGY↗

Single-molecule tracking study of the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene- block -poly(ethylene oxide) films

Understanding the properties of solvent-swollen block copolymer (BCP) microdomains is important for better solvent-based control of microdomain morphology, orientation, and permeability. In this study, single-molecule tracking (SMT) was explored to assess the permeability and transverse width of individual cylindrical microdomains in solvent-swollen polystyrene- block -poly(ethylene oxide) (PS-b-PEO) films. PS-b-PEO films comprising shear-elongated cylindrical PEO microdomains were prepared by sandwiching its benzene or tetrahydrofuran (THF) solution between two glass substrates. In this paper, SMT measurements were performed at different drying times to investigate the effects of solvent evaporation on the microdomain properties. SMT data showed one-dimensional (1D) motions of single fluorescent molecules (sulforhodamine B) based on their diffusion within the cylindrical microdomains. Microdomain permeability and transverse width were assessed from the single-molecule diffusion coefficients (D SMT ) and transverse variance of the 1D trajectories (σ δ 2 ), respectively. The D SMT and σ δ 2 values from individual 1D trajectories were widely distributed with no evidence of correlation on a single molecule basis, possibly because the individual microdomains in a film were swollen to different extents. On average, microdomain permeability (D) and effective radius (r) gradually decreased within the first 3 days of drying due to solvent evaporation, and changed negligibly thereafter. PS-b-PEO films prepared from THF solutions exhibited larger changes in D and r as compared with those from benzene solutions due to the better swelling of the PEO microdomains by THF. Importantly, changes in D were more prominent than those in r, suggesting that the permeability of the PEO microdomains is very susceptible to the presence of solvent. Finally, these results reveal the unique capability of SMT to assess the properties of individual cylindrical microdomains in a solvent-swollen BCP film.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Volatilization Behavior of Supported Au Nanoparticle Arrays under H 2 at High Temperature

In this work, the fabrication and experimental study of model Au nanoparticle arrays (nanodots) was used to allow a direct comparison of reactive evaporation at elevated temperatures and nonambient H 2 -containing gas atmospheres with theoretical models. Strong temperature and H 2 -concentration dependencies were confirmed as expected, and the observed dependence in particle diameter with time was effectively described using a reactive evaporation and gas phase diffusion based quantitative model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Overcoming Variability: A Reproducible Approach to SERS Detection of Nanodiamonds

Detonation nanodiamonds (DNDs) are formed at specific pressures and temperatures during explosions. Different explosives produce varied yields of DNDs within their detonation soot, with Composition B producing the highest yield. Raman spectroscopy (RS) is often used for the characterization of sp 2 - and sp 3 -hybridized carbon allotropes in carbonaceous materials because of distinct disorder and graphitic bands. Bulk diamond also gives a distinct Raman peak at 1332 cm –1 . Furthermore, as bulk diamond decreases in size to nanometer-sized species, the peak red-shifts and broadens, becoming increasingly difficult to detect with RS using visible excitations. Therefore, surface-enhanced Raman spectroscopy (SERS) was used to enhance the diamond peak of DNDs, enabling better detection and faster examination of DNDs within detonation soot. Previous literature of the SERS of DNDs delivered inconsistent results in spectral signatures and SERS substrates. Herein, refining of the methodology for the acquisition of SERS spectra of DNDs was achieved. Before any SERS experiments, the DNDs were first characterized with normal Raman (NR) and scanning electron microscopy. Two routes for SERS enhancement were evaluated: colloidal noble metal nanoparticles and evaporated silver films. Silver films produced the best signal enhancement of DNDs with the best signal-to-noise and peak enhancements observed at 20–30 nm thick silver films at 5% (∼300 μW) laser power. Consistent, reproducible SERS spectra were acquired of small aggregates of DNDs down to ∼500 nm. NR and SERS mapping analysis of DNDs before and after evaporation of silver films revealed the improvements in the detection capabilities of SERS compared with NR.

Carbon↗

A Direct Probe of the Hydrogen Bond Network in Aqueous Glycerol Aerosols

The properties of aerosols are of paramount importance in atmospheric chemistry and human health. The hydrogen bond network of glycerol-water aerosols generated from an aqueous solution with different mixing ratios is probed directly with X-ray photoelectron spectroscopy. The carbon and oxygen X-ray spectra reveal contributions from gas and condensed phase components of the aerosol. It is shown that water suppresses glycerol evaporation up to a critical mixing ratio. A dielectric analysis using terahertz spectroscopy coupled with infrared spectroscopy of the bulk solutions provides a picture of the microscopic heterogeneity prevalent in the hydrogen bond network when combined with the photoelectron spectroscopy analysis. The hydrogen bond network is composed of three intertwined regions. At low concentrations, glycerol molecules are surrounded by water forming a solvated water network. Adding more glycerol leads to a confined water network, maximizing at 22 mol %, beyond which the aerosol resembles bulk glycerol. This microscopic view of hydrogen bonding networks holds promise in probing evaporation, diffusion dynamics, and reactivity in aqueous aerosols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electric-Field Assisted Assembly of Colloidal Particles into Ordered Nonclose-Packed Arrays

Nonclose-packed colloidal arrays have many potential applications ranging from plasmonic sensors, light trapping for photovoltaics, to transparent electrodes. However, scalable fabrication of those structures remains a challenge. In this Article, we investigate the robustness of an electric-field assisted approach systematically. A monolayer of nonclose-packed crystalline array is first created under a low-frequency alternating-current electric field in solution. We then apply a sequence of direct-current pulses to fix the particle array onto the substrate so that it remains intact even after both field removal and solvent evaporation. Key process parameters such as the alternating-current field strength, direct-current magnitude, particle concentration, and solvent-evaporation rate that affect both ordering and fixing of colloidal particles have been studied systematically. Here, we find that direct currents with an intermediate magnitude induce electrophoretic motion of particles toward the substrate and facilitate their permanent adhesion on the substrate due to strong van der Waals attraction. A higher current, however, causes lateral aggregation of particles arising from electroosmotic flow of solvent and destroys the periodic ordering between particles. This approach, in principle, can be conveniently adapted into the continuous convective assembly process, thus making the fabrication of nonclose-packed colloidal arrays scalable.

42 ENGINEERING↗

Direct Observation on Spin-Coating Process of PS- b -P2VP Thin Films

We studied the structural development of symmetric poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) block copolymers during spin-coating using in situ grazing incidence small angle X-ray scattering (GISAXS) measurements. During the spin-coating process, after the formation of the micelles in dilute solution, the selective solvent induced two kinds of the morphological transition. Firstly, the disordered spherical micelles were transformed into a BCC lattice of spheres of which the (110) plane was oriented perpendicularly to the substrate surface. Secondly, further evaporation induced a transition from spheres on the BCC lattice into cylindrical structures. The orientation of the cylinders perpendicular to the substrate surface was induced by solvent convection perpendicular to the substrate, which occurs during rapid solvent evaporation. After this transition, vitrification of PS and P2VP prevented any further transition from cylinders to the more thermodynamically stable lamellar structures, as are generally observed as the bulk equilibrium state.

block copolymer thin films↗

Reversible, Tunable, Electric-Field Driven Assembly of Silver Nanocrystal Superlattices

Nanocrystal superlattices are typically fabricated by either solvent evaporation or destabilization methods that require long time periods to generate highly ordered structures. In this paper, we report for the first time the use of electric fields to reversibly drive nanocrystal assembly into superlattices without changing solvent volume or composition, and show that this method only takes 20 min to produce polyhedral colloidal crystals, which would otherwise need days or weeks. This method offers a way to control the lattice constants and degree of preferential orientation for superlattices and can suppress the uniaxial superlattice contraction associated with solvent evaporation. As a result, in situ small-angle X-ray scattering experiments indicated that nanocrystal superlattices were formed while solvated, not during drying.

36 MATERIALS SCIENCE↗