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At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Combinatorial Block Copolymer Ordering on Tunable Rough Substrates

Morphology control of block copolymer (BCP) thin films through substrate interaction via controlled roughness parameters is of significant interest for numerous high-tech applications ranging from solar cells to high-density storage media. While effects of substrate surface energy (SE) and roughness (R) on BCP morphology have been individually investigated, their synergistic effects have not been explored in any systematic manner. Interestingly, orientation response of BCP to changes in SE can be similar to what can be accomplished with variations in R. Here we present a novel approach for orienting lamellar BCP films of poly(styrene)-block-poly(methyl methacrylate) (PS-PMMA) on spin-coated xerogel (a dried gel of silica nanoparticle network) substrate with simultaneously tunable surface energy, {gamma}{sub s} {approx} 29-53 mJ/m{sup 2}, by UVO exposure and roughness, R{sub rms} {approx} 0.5-30 nm, by sol-gel processing steps of regulating the catalyst concentration and sol aging time. As in previous BCP orientation studies on 20 nm diameter monodisperse silica nanoparticle coated surface, we find a similar but broadened oscillatory BCP orientation behavior with film thickness due to the random rather than periodic rough surfaces. We also find that higher random roughness amplitude is not the necessary criteria for obtaining a vertical orientation of BCP lamellae. Rather, a high surface fractal dimension (D{sub f} > 2.4) of the rough substrate in conjunction with an optimal substrate surface energy {gamma}{sub s} {approx} 29 mJ/m{sup 2} results in 100% vertically oriented lamellar microdomains. The AFM measured film surface microstructure correlates well with the internal 3D BCP film structure probed by grazing incidence small-angle X-ray scattering (GISAXS) and rotational small-angle neutron scattering (SANS). In contrast to tunable self-assembled monolayer (SAM)-coated substrates, the xerogel films are very durable and retain their chemical properties over period of several months. These results also highlight importantly that BCP orientation control for nanotechnology is possible not only on specially prepared patterned substrates but also on industrially viable sol-gel substrates.

14 SOLAR ENERGY↗
DOE OSTI2012

A Stepwise "Micellization-Crystallization" Route to Oblate Ellipsoidal, Cylindrical, and Bilayer Micelles with Polyethylene Cores in Water

Micellar polymorphism from block copolymers has been well documented, but most attention has focused on noncrystalline hydrophobic systems. We have investigated the micellization in water of model diblock copolymers with semicrystalline polyethylene (PE) as the core-forming component. Poly(N,N-dimethylacrylamide)–polyethylene (AE) diblock copolymers were synthesized by a combination of anionic and RAFT polymerizations. The bulk nanostructures were probed by small-angle X-ray scattering (SAXS) and AE diblock copolymers were found to be moderately segregated at 140 °C. Dispersions of AE amphiphiles in water were prepared by direct dissolution at 120 °C (i.e., above the melting transition of PE) followed by cooling to 25 °C. By manipulating the composition of AE diblock copolymers, discrete structures with oblate ellipsoidal, cylindrical, and bilayer morphologies were produced, as evidenced in cryogenic transmission electron microscopy (cryo-TEM). The self-assembled aggregates were also studied by small-angle neutron scattering (SANS) and dilute solution rheology. The semicrystalline nature of the nanostructures was further revealed by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). A stepwise “micellization–crystallization” process was proposed as the micelle formation mechanism, as supported by the existence of similar nanostructures at 120 °C using SANS. This strategy holds promise for a general protocol toward the production of giant wormlike micelles and vesicles with semicrystalline polymeric cores.

Yin, Ligeng↗
DOE OSTI2013

Multicompartmental Microcapsules from Star Copolymer Micelles

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into the LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Train Traffic as a Powerful Noise Source for Monitoring Active Faults With Seismic Interferometry

Laboratory experiments report that detectable seismic velocity changes should occur in the vicinity of fault zones prior to earthquakes. However, operating permanent active seismic sources to monitor natural faults at seismogenic depth is found to be nearly impossible to achieve. We show that seismic noise generated by vehicle traffic, and especially heavy freight trains, can be turned into a powerful repetitive seismic source to continuously probe the Earth's crust at a few kilometers depth. Results of an exploratory seismic experiment in Southern California demonstrate that correlations of train-generated seismic signals allow daily reconstruction of direct P body waves probing the San Jacinto Fault down to 4-km depth. This new approach may facilitate monitoring most of the San Andreas Fault system using the railway and highway network of California.

58 GEOSCIENCES↗
DOE OSTI2020

Efficient Nighttime Biogenic SOA Formation in a Polluted Residual Layer

Abstract Organic nitrates formed from nighttime reaction between anthropogenic nitrate radicals (NO3) and biogenic volatile organic compounds (BVOCs) are potentially an important but highly uncertain source of secondary organic aerosol (SOA). Here we report on the enhanced nighttime biogenic SOA formation observed in a polluted residual layer over Sacramento, California, the morning of 15 June 2010 during the Carbonaceous Aerosols and Radiative Effects Study (CARES). Trajectory analysis showed that the residual layer air, containing trace amounts of isoprene and monoterpenes left over after nighttime oxidation, was influenced by the San Francisco Bay Area emissions the previous evening. The residual layer aerosol was also enriched in nitrate, with about 64% of it estimated to be in the form of organic nitrates. The nitrate:organic mass ratio of the SOA was about 0.47±0.044, which corresponds to the range typically found in isoprene mononitrates. Assuming the SOA was composed of organic mononitrates, its nominal molecular weight was estimated at 186±11 g mol-1, consistent with the highly functionalized isoprene hydroxynitrates that have been observed in the particle phase in the southeast United States. Overall, our findings show that the efficiency of nighttime biogenic SOA formation, expressed as the change in organic aerosol mass relative to carbon monoxide (?OA/?CO), was about 100 µg m-3 ppmv, which falls in the range 77-157 µg m-3 ppmv previously estimated for enhanced daytime SOA formation from mixed anthropogenic and biogenic emissions during CARES.

Zaveri, Rahul A.↗
DOE OSTI2022

Seeking Repeating Anthropogenic Seismic Sources: Implications for Seismic Velocity Monitoring at Fault Zones

Abstract Seismic velocities in rocks are highly sensitive to changes in permanent deformation and fluid content. The temporal variation of seismic velocity during the preparation phase of earthquakes has been well documented in laboratories but rarely observed in nature. It has been recently found that some anthropogenic, high‐frequency (>1 Hz) seismic sources are powerful enough to generate body waves that travel down to a few kilometers and can be used to monitor fault zones at seismogenic depth. Anthropogenic seismic sources typically have fixed spatial distribution and provide new perspectives for velocity monitoring. In this work, we propose a systematic workflow to seek such powerful seismic sources in a rapid and straightforward manner. We tackle the problem from a statistical point of view, considering that persistent, powerful seismic sources yield highly coherent correlation functions (CFs) between pairs of seismic sensors. The algorithm is tested in California and Japan. Multiple sites close to fault zones show high‐frequency CFs stable for an extended period of time. These findings have great potential for monitoring fault zones, including the San Jacinto Fault and the Ridgecrest area in Southern California, Napa in Northern California, and faults in central Japan. However, extra steps, such as beamforming or polarization analysis, are required to determine the dominant seismic sources and study the source characteristics, which are crucial to interpreting the velocity monitoring results. Train tremors identified by the present approach have been successfully used for seismic velocity monitoring of the San Jacinto Fault in previous studies.

58 GEOSCIENCES↗
DOE OSTI2011

2D-Ising critical behavior in mixtures of water and 3-methylpyridine

The effect of an antagonistic salt on the phase behavior and nanoscale structure of a mixture of D{sub 2}O and 3-methylpyridine was investigated by visual inspection and small-angle neutron scattering (SANS). The addition of the antagonistic salt, namely sodium tetraphenylborate (NaBPh{sub 4}), induces the shrinking of the two-phase region in contrast to the case in which a normal (hydrophilic) salt is added. Below the phase separation point, the SANS profiles cannot be described by the Ornstein-Zernike function owing to the existence of a long-range periodic structure. With increasing salt concentration, the critical exponents change from the values of 3D-Ising and approach those of 2D-Ising. These results suggest that the concentration fluctuation of the mixture of solvents is limited to a quasi two-dimensional space by the periodic structure induced by the adding the salt. The same behaviors were also observed in mixtures composed of water, 3-methylpyridine, and ionic surfactant.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2014

Structural and mechanical properties of cardiolipin lipid bilayers determined using neutron spin echo, small angle neutron and X-ray scattering, and molecular dynamics simulations

We report that the detailed structural and mechanical properties of a tetraoleoyl cardiolipin (TOCL) bilayer were determined using neutron spin echo (NSE) spectroscopy, small angle neutron and X-ray scattering (SANS and SAXS, respectively), and molecular dynamics (MD) simulations. We used MD simulations to develop a scattering density profile (SDP) model, which was then utilized to jointly refine SANS and SAXS data. In addition to commonly reported lipid bilayer structural parameters, component distributions were obtained, including the volume probability, electron density and neutron scattering length density.

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

Aggregation of cyclic polypeptoids bearing zwitterionic end-groups with attractive dipole–dipole and solvophobic interactions: a study by small-angle neutron scattering and molecular dynamics simulation

Aggregation behavior of cyclic polypeptoids bearing zwitterionic end-groups in methanol has been studied using a combination of experimental and simulation techniques. Here, the data from SANS and cryo-TEM indicate that the solution contains small clusters of these cyclic polypeptoids, ranging from a single polypeptoid chain to small oligomers, while the linear counterpart shows no cluster formation. Atomistic molecular dynamics simulations reveal that the driving force for this clustering behavior is due to the interplay between the effective repulsion due to the solvation of the dipoles formed by the charged end-groups in each polypeptoid chain and the attractive forces due to dipole–dipole interactions and the solvophobic effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Electric field directed formation of aligned conjugated polymer fibers

Alternating current (AC) electric fields effectively align poly (3-alkylthiophene) (P3AT) fibers during a one-dimensional crystallization process. Structural, mechanical and electrical properties have been probed using microscopy, small angle neutron scattering (SANS), atomic force microscopy (AFM), x-ray diffraction (XRD), rheology, UV-vis spectroscopy, and dielectric spectroscopy. Optimum frequency and amplitudes were identified for specific P3AT concentrations and for variable solvent quality. Optical microscopy along with SANS and XRD demonstrate alignment persists over both micrometer and nanometer length scales. Small amplitude oscillatory shear rheology also showed that the shear modulus increased for aligned fibers. The structural changes were correlated to improvements in electric conductivity as probed by dielectric spectroscopy. XRD experiments performed with variable sample orientations also showed that the P3HT stacking direction was aligned parallel to the direction of the fiber axis. Electric field alignment was also possible for other alkyl-thiophene polymers and for polymers with simple backbone repeat units.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Small-angle neutron scattering study of a dense microemulsion system formed with an ionic liquid

Mixtures of water, octane and 1-octanol with 1-tetradecyl-3-methylimidazolium chloride (C14MIM·Cl), often referred to as a surface active ionic liquid (SAIL), form water-in-oil microemulsions that have potential application as extraction media for various metal ions. Here in this work, we present a structural study by small-angle neutron scattering (SANS) of dense microemulsions formed by surfactant-rich mixtures of these four compounds to understand how the SAIL can be used to tune the structures and properties of the microemulsions. The SANS experiments revealed that the microemulsions formed are composed of two phases, a water-in-oil microemulsion and a bicontinuous microemulsion, which becomes the dominant phase at high surfactant concentration. In this concentration regime, the surfactant film becomes more rigid, having a higher bending modulus that results from the parallel stacking of the imidazolium ring of the SAIL. At lower surfactant concentrations, the molecular packing of the SAIL does not change with the water content of the microemulsion. Finally, the results presented here correlate well with previously observed changes in the interaction between the IL cation and metal ions (Y. Tong, L. Han and Y. Yang, Ind. Eng. Chem. Res., 2012, 51, 16438–16443), while the capacity of the microemulsion system for water remains high enough for using the system as an extraction medium.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering

The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Observation of a structural gradient in Winsor-III microemulsion systems

Here, we demonstrate here for the first time via small-angle neutron scattering (SANS) that the middle, bicontinuous microemulsion (BμE) phase of Winsor-III systems undergoes a gradual change of structure and composition in the vertical direction, contrary to the commonly held belief of uniform structure and composition. A vertical stage was deployed to enable precise alignment of a custom-designed rectangular cell containing the W III system with respect to the neutron beam, allowing for several different vertical positions to be analyzed. For the water/AOT/CK-2,13 (two-tailed alkyl ethoxylate containing a 1,3-dioxolane linkage)/heptane Winsor-III system, the quasi-periodic repeat distance ( d ) and correlation length (ξ), obtained from the Teubner–Strey model applied to the SANS data, decreased and the surface area per volume of the surfactant monolayer ( via Porod analysis) increased in the downward direction, trends that reflect an increase of surfactant concentration, consistent with the ultralow interfacial tension that often occurs for the lower liquid–liquid interface of many W III systems. The water/sodium dodecyl sulfate (SDS)/1-pentanol/dodecane system shared the same trend with regard to d as observed for AOT/CK-2,13. In contrast, for SDS/pentanol, ξ increased and the amphiphilicity factor ( f a ) decreased in the downward direction, trends consistent with a decrease of cosurfactant (pentanol) concentration in the downward direction. Non-uniformity in the vertical direction has implications in the transport of solutes between W III phases during the extractive purification of proteins or the removal of heavy metals and pollutants from wastewater, or the deposition of BμEs onto hydrophilic vs. hydrophobic surfaces as thin coatings.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Sonocrystallization of conjugated polymers with ultrasound fields

Ultrasound acoustic waves are demonstrated to assemble poly-3-hexylthiophene (P3HT) chains into nanofibers after they are fully dissolved in what are commonly considered to be ‘good’ solvents. In the absence of ultrasound, the polymer remains fully dissolved and does not selfassemble for weeks. UV-vis spectroscopy, ultra-small angle x-ray scattering (USAXS) and small angle neutron scattering (SANS) are used to characterize the induced assembly process and to quantify the fraction of polymer that forms nanofibers. It is determined that the solvent type, insonation time, and aging periods are all important factors affecting the structure and final concentration of fibers. The effect of changing polymer regio-regularity, alkyl chain length, and side chain to thiophene ratio are also explored. High intensity focused ultrasound (HIFU) fields of variable intensity are utilized to reveal the physical mechanisms leading to nanofiber formation, which is strongly correlated to cavitation events in the solvent. This in-situ HIFU cell, which is designed for simultaneous scattering analysis, is also used to probe for structural changes occurring over multiple length scales using USAXS and SANS. The proposed acoustic assembly mechanism suggests that, even when dispersed in ‘good’ solvents such as bromobenzene, dichlorobenzene and chloroform, P3HT chains are still not in a thermodynamically stable state. Instead, they are stabilized by local energy barriers that slow down and effectively prevent crystallization. Ultrasound fields are found to provide enough mechanical energy to overcome these barriers, triggering the formation of small crystalline nuclei that subsequently seed the growth of larger nanofibers.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Investigating the effect of supramolecular gel phase crystallization on gel nucleation

Supramolecular gel phase crystallization offers a new strategy for drug polymorph screening and discovery. In this method, the crystallization outcome depends on the interaction between solute and gel fibre. While supramolecular gels have shown success in producing new polymorphs and crystals with novel morphologies, role of the gel and nature of gel–solute interaction remains largely unexplored. The present study aims to provide a comprehensive picture of the structural evolution of a supramolecular gel produced from a bis(urea) based gelator (G) in the presence of a polymorphic drug carbamazepine (CBZ). The structural aspects of the gel have been assessed by single crystal X-ray analysis, X-ray powder diffraction (XRPD) and solid state NMR spectroscopy. Small Angle Neutron Scattering (SANS) has been used to follow the changes in gel structure in the presence of CBZ. Visual evidence from morphological study and structural evolution observed at a macroscopic level from rheological measurements, shows good agreement with the SANS results. The concentration of the gelator and the relative proportion of G to CBZ were found to be crucial factors in determining the competitive nucleation events involving gelation and crystallization. At a critical G to CBZ ratio the effect of CBZ on gel structure was maximum and fiber bundling in the gel was found to be critically affected. Here, this study offers important information about how the interplay of gelator assembly and gel–solute interactions can fine-tune the nucleation events in a supramolecular gel phase crystallization.

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

Influence of NaCl on shape deformation of polymersomes

Polymersomes frequently appear in the literature as promising candidates for a wide range of applications from targeted drug delivery to nanoreactors. From a cell mimetic point of view, it is important to understand the size and shape changes of the vesicles in the physiological environment since that can influence the drug delivery mechanism. In this work we studied the structural features of polymersomes consisting of poly(ethylene glycol)–poly(dimethylsiloxane)–poly(ethylene glycol) at the nanoscopic length scale in the presence of NaCl, which is a very common molecule in the biotic aqueous environment. Here, we used dynamic light scattering (DLS), cryo-TEM, small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS). We observed transformation of polymersomes from spherical to elongated vesicles at low salt concentration and into multivesicular structures at high salt concentration. Model fitting analysis of SANS data indicated a reduction of vesicle radius up to 47% and from the SAXS data we observed an increase in membrane thickness up to 8% and an increase of the PDMS hydrophobic segment up to 11% indicating stretching of the membrane due to osmotic imbalance. Also, from the increase in the interlamellar repeat distance up to 98% under high salt concentrations, we concluded that the shape and structural changes observed in the polymersomes are a combined result of osmotic pressure change and ion–membrane interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Diffusion characteristics of water molecules in a lamellar structure formed by triblock copolymers

The distribution and diffusion of water molecules are playing important roles in determining self-assembly and transport properties of polymeric systems. Small-angle neutron scattering (SANS) experiments and molecular dynamics (MD) simulation have been applied to understand the distribution of water molecules and their dynamics in the lamellar membrane formed by Pluronic L62 block copolymers. Penetration of water molecules into the polyethylene oxide (PEO) layers of the membranes has been estimated using scattering length density (SLD) profiles obtained from SANS measurements, which agree well with the molecular distribution observed from MD simulations. The water diffusion coefficient at different regions of the lamellar membrane was further investigated using MD simulation. The diffusion characteristic shows a transition from normal to anomalous diffusion as the position of the water molecule changes from the bulk to PEO and to the polypropylene oxide (PPO) layer. Here we find that water molecules within the PEO or PPO layers follow subdiffusive dynamics, which can be interpreted by the model of fractional Brownian motion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗