Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ROUGHNESS”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Localization of Nonblinking Point Sources Using Higher-Order-Mode Detection and Optical Heterodyning: Developing a Strategy for Extending the Scope of Molecular, Super-resolution Imaging

While the stochastic, “blinking” nature of fluorescent systems has enabled the super-resolution of their localization by the fitting of their point-spread functions (PSFs), this strategy cannot be exploited for similar resolution of “nonblinking” systems, such as those that might be encountered in a coherent Raman experiment. An alternative method for subdiffraction-limited imaging lies in the exploitation of optical heterodyning. For example, if a Gaussian PSF (a TEM00 mode) of a point emitter is displaced with respect to the origin of the optical system, photons in the higher-order TEM modes carry information about that displacement. Information concerning the displacement can be extracted from photons in these higher-order modes. These photons can be collected by optical heterodyning, which exploits the large gain in a detector’s response to an optical signal from an emitter coupled to a local oscillator, which is prepared in the TEM of interest, e.g., TEM10. We have generalized and developed the heterodyning technique to localize point emitters via the detection of higher-order spatial modes. We have developed a theoretical approach to find a practical estimation limit of the localization parameters using a realistic model that accounts for shot noise, background noise, and Gaussian noise. To demonstrate the applicability of the method, we designed experiments in which a laser is a surrogate for one and two point emitters. Using the Fisher information and its accompanying Cramér-Rao lower bound, we demonstrate super-resolution localization in these cases: we show that objects can be localized to roughly 2–3 orders of magnitude of their point-spread function’s size for a given optical system. Finally and most importantly, it is suggested that the results will ultimately be generalizable to multiple emitters and, most importantly, to “nonblinking” molecular systems, which will be essential for broadening the scope of super-resolution measurements beyond the limits of fluorescence-based techniques.

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

Complex Formation and Dissociation Dynamics on Amorphous Silica Surfaces

Benzene complex formation and dissociation dynamics with silanols on the amorphous silica surfaces of nanoporous SiO 2 , from a benzene/carbon tetrachloride solution, were measured by the growth of off-diagonal peaks in the two dimensional infrared (2D IR) chemical exchange spectrum of the isolated Si-OD stretch. The presence of two types of isolated silanols, referred to as type I and II, was revealed, with dissociation time constants of 82 ps and 4.0 ps for type I and II complexes, respectively. The type I silanols are associated with the main IR absorption feature in the Si-OD stretching region, while the type II silanols give rise to a broader shoulder to lower frequency. Polarization selective pump-probe (PSPP) measurements provided the vibrational lifetimes and orientational relaxation rates of the two silanols in the CCl 4 (free) and benzene (complex) environments. The type II silanols constitute roughly 30% of the isolated silanol population and exhibit a substantially faster rate of vibrational relaxation, making the type I dynamics the dominant contribution to the PSPP and 2D IR signals. From the measured dissociation times, the enthalpies of formation for the two surface complexes were obtained; the formation of the type I complex being significantly more exothermic. Furthermore, as the type II site is preferentially removed from the amorphous silica surface with increasing activation temperature, the results provide a reasonable explanation for the increased exothermicity of benzene adsorption on silica with increasing activation temperature in previous calorimetry experiments.

14 SOLAR ENERGY↗
DOE OSTI2021

Electron-Induced Proton Transfer

The pathway of activationless proton transfer induced by an electron-transfer reaction is studied theoretically. Long-range electron transfer produces highly nonequilibrium medium polarization that can drive proton transfer through an activationless transition during the process of thermalization, dynamically altering the screening of the electron–proton Coulomb interaction by the medium. The cross electron–proton reorganization energy is the main energy parameter of the theory, which exceeds in magnitude the proton-transfer reorganization energy roughly by the ratio of the electron-transfer to proton-transfer distance. This parameter, which can be either positive or negative, is related to the difference in pK a values in two electron-transfer states. The relaxation time of the medium is on the (sub)picosecond time scale, which establishes the characteristic time for activationless proton transfer. Microscopic calculations predict substantial retardation of the collective relaxation dynamics compared to the continuum estimates due to the phenomenology analogous to de Gennes narrowing. As a result, nonequilibrium medium configuration promoting proton transfer can be induced by either thermal or photoinduced charge transfer.

14 SOLAR ENERGY↗
DOE OSTI2025

Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid–Liquid Extraction System

Organic phase aggregation and phase splitting are two important (and connected) phenomena in liquid–liquid extraction of metal ions. Previously, we demonstrated how structure in binary mixtures of extractant and diluent originates from concentration fluctuations associated with the so-called “third-phase formation” liquid–liquid phase instability. For more complex systems, we sought to understand how extracted aqueous components affect these concentration fluctuations. Here, in this study, we use small-angle X-ray scattering and molecular dynamics simulations to investigate organic phase structural changes upon contact with water in a model ternary system of water/alkane/extractant. Critical exponents were determined from scattering with temperature variation and were consistent with mean field values. Then, by controlling the water content in the organic phase through direct dissolution of fixed quantities at constant temperature, we relate the observed increase in the fluctuation length scale to changes to the spinodal temperature of the third-phase formation phase boundary. We find a roughly linear relationship between water concentration and the spinodal temperature and a similar slope in that relationship for different linear alkane diluents. This suggests that the mechanism by which water extraction impacts the organic phase structure is to enhance concentration fluctuations through the introduction of additional polar extractant-water complexes, which increases the spinodal temperature and thereby decreases the reduced temperature, i.e., the distance to the instability. This explanation for how solutes induce aggregation in liquid–liquid extraction organic phases may extend to more complex systems, explaining the large increases in correlation lengths reported under high acid and metal loading.

Bonnett, Brittany L. [Argonne National Laboratory ↗
DOE OSTI2021

Local Lattice Deformation of Tellurene Grain Boundaries by Four-Dimensional Electron Microscopy

Two-dimensional (2D) tellurene is a promising competitor for the fabrication of ultrathin optoelectronic devices belonging to a new family of monoelemental 2D materials. Furthermore, the precise fabrication and characterization of tellurene and its lattice defects is of utmost importance to determine device reliability and predict functionality, yet it remains experimentally challenging. The rapid growth of the four-dimensional scanning transmission electron microscopy (4D-STEM) technique as well as postprocessing tools now allows for structural analysis with nanometer-scale resolution over a broad range of length scales. Here, we use 4D-STEM to reveal the three-dimensional (3D) atomic structure of the characteristic grain boundary in 2D tellurium formed through a new microwave-enabled chemical self-assembly. Strain and lattice parameter maps permit the reconstruction of the roughness of the grain boundary and suggest that its formation is promoted by a wedge of helical atomic chains along the [0001] crystallographic direction. The observation of wrinkles at the grain boundary is found to be the dominant relaxation mechanism. Insights into the formation mechanism are elucidated by mapping the lattice parameters as the first demonstration of local in-plane and out-of-plane unit cell variation in a nanometer-by-nanometer real-space array.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomic-Scale STEM Analysis Shows Structural Changes of Au–Pd Nanoparticles in Various Gaseous Environments

We report dynamical restructuring effects in free-standing Au 0.75 Pd 0.25 nanoparticles occurring in gaseous environments at elevated temperatures. The freshly prepared sample was found to have a core–shell structure with a Pd-rich phase on the surface. The evolution of sample composition and morphology under exposure to 1 bar of pure gases, namely O 2 , H 2 , air, CO, and CO 2 , at different temperatures was studied using in situ scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS). We observed sharper facets on the surface of the particles under O 2 or air at 400 °C. Small islands of Pd were present on the surface, although some Pd was redistributed inside the bulk when the temperature was increased under O 2 . Subtle changes in surface roughness were noted when O 2 was substituted with H 2 at 400 °C, an observation correlated to density functional theory (DFT) calculations. The particles lost clean surface facets when CO was introduced at room temperature and at 200 °C. No substantial changes could be observed after exposure to CO 2 at 250 °C. The adsorption of CO molecules on the surface modifies the surface of the particles and decreases the facet prevalence. Furthermore, these in situ observations show how gases can induce subtle modification of the surface of nanocatalysts, potentially impacting their chemical properties.

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

Dynamics of Electric Polarization and Relaxation of Ions at Humid Calcite Surfaces

Mobile ions at mineral surfaces can respond to an applied electric field, adopting a new distribution that effectively represents polarization of the electrical double layer. When the field is released, the ions relax to their equilibrium distribution. In both cases, the dynamics are characteristic of the interface. However, current models of electrokinetic phenomena are not sufficiently robust to accurately predict collective ion dynamics at structurally and chemically specific mineral–water interfaces. Here, in this study, we use electrostatic force microscopy (EFM) to investigate the dynamics of ion relaxation at hydrated calcite (104) surfaces at controlled relative humidity (RH). Electrically biased probes are used to polarize the distributions of calcium and carbonate ions that are intrinsic to this interface across a range of RH values. Polarization kinetics are tracked by monitoring the tip–sample force gradient during charging, and EFM imaging is used to characterize the spatial relaxation dynamics after the applied field is released. Electrostatic finite element modeling of the sample/probe system across length-scales from nanometers to millimeters reproduces the observed stretched exponential charging response. Together, these results allow us to estimate the ion diffusivities at the interface across a wide range of RH values. These diffusivities increase by roughly 5 orders of magnitude as the RH is increased from 5 to 90%, highlighting the critical role of adsorbed water for surface ion solvation that enables ion mobility.

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

Open Circuit Potential of a Au Catalyst during Selective Oxidation of Glycerol

It has been of great interest to understand relationships between the potential of a metal catalyst and its thermochemical catalytic activity, especially in an aqueous phase environment. In the literature, there are correlations of open circuit potential with reaction rates or surface concentrations of reaction intermediates. In this study, we measured the open circuit potential (OCP) of a Au gauze during selective oxidation of glycerol to glyceric acid and hydrogen peroxide in a basic solution, as a function of hydroxide and alcoholate concentrations. It is found that applying a potential to the Au catalyst has no influence on the reaction rate. Although a rough correlation appears to exist between OCP and reaction rate, the data are better fit to an equation which assumes that the potential of the metal (i.e. the OCP) is in equilibrium with the electrochemical potential of the solution, which is defined by the thermodynamic activities of the oxidizing and reducing species. The equation: OCP = constant + Σ ox [(RT/FZ ox )ln[Ox]] - Σ red [(RT/FZ red )ln[Red]] implicitly assumes that the Au metal functions as a probing electrode. It is further found that this equation also applies to the Au-catalyzed H 2 O 2 oxidation/decomposition reaction in a basic medium, and possibly to formic acid dehydrogenation. Here, we postulate that the apparent correlation between OCP and reaction rate is due to the fact that the reaction rate is proportional to the concentrations of the reaction products and/or reactants that define the electrochemical potential of the solution.

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

New Insights into Nonthermal Plasma-Assisted Poly(vinyl alcohol) Depolymerization Catalyzed by TiO 2

Here, in this study, we investigated the solid residual poly(vinyl alcohol) (PVA) and TiO 2 after nonthermal air, CO 2 , and N 2 plasma depolymerization in the absence and presence of TiO 2 . Scanning electron microscopy studies showed the absence of highly viscous tar and carbonaceous residues on the surfaces of PVA and TiO 2 . In the absence of TiO 2 , PVA particles exhibited micron-sized holes on their surfaces, whereas in the presence of TiO 2 , the surface roughness of PVA particles was observed at the submicron scale. These observations suggest that TiO 2 facilitates the even distribution of nonthermal plasma at a submicron scale, leading to a more uniform depolymerization of PVA surfaces. Raman, Fourier transform infrared spectroscopy, and X-ray absorption spectroscopy showed that (i) the surface of residual PVA contains mainly ketone functional groups and less C-H bonds than the pristine PVA and (ii) further confirmed the absence of highly viscous tar and carbonaceous residues on both used TiO 2 and residual PVA. The nuclear magnetic resonance and mass spectroscopy suggested that the PVA is growing back to poly polyvinyl acetate by the esterification reaction, and the ethers are produced by the acetal reaction between PVA and aldehyde. The transmission electron microscopy and X-ray diffraction analysis indicated no major crystal structural change of the TiO 2 catalyst after the plasma reactions. This study demonstrates that nonthermal plasma-assisted depolymerization is a viable alternative to thermal depolymerization, offering the unique advantage of converting polymer wastes into gaseous small organic molecules without generating recalcitrant viscous tar and carbonaceous residues on the surfaces of the polymer and TiO 2 catalysts.

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

Controlling Preferred Grain Orientation in Vapor-Deposited Metal-Halide Perovskite Thin Films

Metal-halide perovskites are promising semiconductor materials for light-absorber layers in solar cells due to their optimized band gap, defect tolerance, and relative ease of synthesis. In this work, we demonstrate the viability of vapor transport deposition (VTD), a solvent-free processing method, to realize polycrystalline films of both lead iodide (PbI 2 ) and methylammonium lead iodide (MAPbI 3 ) perovskites showing preferential crystallographic orientation. Notable is the difference in perovskite film texturing observed for sequentially and co-deposited VTD films of MAPbI 3 , as well as the lack of strong preferential orientation in solution-processed MAPbI 3 films. While sequential deposition of the perovskite precursors PbI 2 and methylammonium iodide (MAI) leads to a MAPbI 3 film with a limited preferential grain orientation, co-deposited MAPbI 3 films mirror the orientation of excess PbI 2 present in the film. The latter is confirmed by the similar dependence of preferential orientation for PbI 2 and co-deposited MAPbI 3 on underlayer roughness, as well as the emergence of preferential orientation in MAPbI 3 only when excess PbI 2 is present. Both MAPbI 3 and PbI 2 films show a strong preferred lattice orientation on smooth substrates, while on rougher substrates, this orientation is disrupted. Furthermore, these results are interpreted as excess PbI 2 frustrating the diffusion of MAI in the film, which would otherwise disrupt the preferred orientation, pointing to a notable difference in lattice orientation arising from processing technique and conditions.

Deposition↗
DOE OSTI2026

Super-Resolved Single-Molecule Tracking Studies of Rhodamine B Accumulation on Fresh and Aged Polyethylene Terephthalate

It is well-known that toxic organic micropollutants (OMs) accumulate on the surfaces of microplastics. However, much remains to be learned about the exact molecular level mechanisms of OM accumulation and how these evolve as the plastics age. In this work, super-resolved single-molecule tracking (SMT) is used for the first time to investigate the accumulation of Rhodamine B (RhB) dye on fresh and artificially aged polyethylene terephthalate (PET) surfaces. PET thin films serve as models for microplastics, while RhB serves as a proxy for the OMs they accumulate. Artificial aging of the films is accomplished by exposing them in a UV-ozone chamber. Water contact angle, spectroscopic ellipsometry, and carbonyl index measurements reveal a gradual decrease in film hydrophobicity, thickness, and carbonyl content with age. Atomic force microscopy (AFM) data reveal an increase in surface roughness and confirm that the films remain largely intact and continuous across the aging times explored. In SMT experiments, wide-field fluorescence videos acquired from the water/PET interface under 7.5 pM RhB reveal both mobile and immobile dye molecules. Measurements of the frame-to-frame displacements of the dye show that diffusion occurs by a desorption-mediated mechanism and that the diffusion rate varies with PET film age. The surface density of mobile dye molecules decreases with increasing PET age, while the population of immobile molecules becomes relatively larger, suggesting an age-dependent transformation of the mechanism(s) by which the dye is accumulated. SMT data reveal that both mobile and immobile molecules repeatedly adsorb over the same surface sites, consistent with the emergence of nanoscale PET surface heterogeneity also revealed by AFM. Estimates of the adsorption coefficients are obtained using a nearest-neighbor analysis, giving values from 9.9 × 10 5 to 2.1 × 10 6 M –1 for immobile molecules and from 1.8 × 10 5 to 2.5 × 10 5 M –1 for mobile molecules on fresh and 5 min aged PET, respectively. Here, anomalous age-dependent variations in the velocity of molecular motion on the PET surface and in the population of immobile molecules are shown to correlate with changes in the strength of RhB adsorption.

Adsorption↗
DOE OSTI2022

Quantum Simulations of Vibrational Strong Coupling via Path Integrals

A quantum simulation of vibrational strong coupling (VSC) in the collective regime via thermostated ring-polymer molecular dynamics (TRPMD) is reported. For a collection of liquid-phase water molecules resonantly coupled to a single lossless cavity mode, the simulation shows that as compared with a fully classical calculation, the inclusion of nuclear and photonic quantum effects does not lead to a change in the Rabi splitting but does broaden polaritonic line widths roughly by a factor of 2. Moreover, under thermal equilibrium, both quantum and classical simulations predict that the static dielectric constant of liquid water is largely unchanged inside vs outside the cavity. Furthermore, this result disagrees with a recent experiment demonstrating that the static dielectric constant of liquid water can be resonantly enhanced under VSC, suggesting either limitations of our approach or perhaps other experimental factors that have not yet been explored.

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

Reaction of Hydrazine with Solution- and Vacuum-Prepared Selectively Terminated Si(100) Surfaces: Pathways to the Formation of Direct Si–N Bonds

Here, the reactivity of liquid hydrazine (N 2 H 4 ) with respect to H-, Cl-, and Br-terminated Si(100) surfaces was investigated to uncover the principles of nitrogen incorporation into the interface. This process has important implications in a wide variety of applications, including semiconductor surface passivation and functionalization, nitride growth, and many others. The use of hydrazine as a precursor allows for reactions that exclude carbon and oxygen, the primary sources of contamination in processing. In this work, the reactivity of N 2 H 4 with H- and Cl-terminated surfaces prepared by traditional solvent-based methods and with a Br-terminated Si(100) prepared in ultrahigh vacuum was compared. The reactions were studied with X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy, and the observations were supported by computational investigations. The H-terminated surface led to the highest level of nitrogen incorporation; however, the process proceeds with increasing surface roughness, suggesting possible etching or replacement reactions. In the case of Cl-terminated (predominantly dichloride) and Br-terminated (monobromide) surfaces, the amount of nitrogen incorporation on both surfaces after the reaction with hydrazine was very similar despite the differences in preparation, initial structure, and chemical composition. Density functional theory was used to propose the possible surface structures and to analyze surface reactivity.

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

Are Contact Angle Measurements Useful for Oxide-Coated Liquid Metals?

This work establishes that static contact angles for gallium-based liquid metals have no utility despite the continued and common use of such angles in the literature. In the presence of oxygen, these metals rapidly form a thin (~1–3 nm) surface oxide “skin” that adheres to many surfaces and mechanically impedes its flow. This property is problematic for contact angle measurements, which presume the ability of liquids to flow freely to adopt shapes that minimize the interfacial energy. We show here that advancing angles for a metal are always high (>140°)—even on substrates to which it adheres—because the solid native oxide must rupture in tension to advance the contact line. The advancing angle for the metal depends subtly on the substrate surface chemistry but does not vary strongly with hydrophobicity of the substrate. During receding measurements, the metal droplet initially sags as the liquid withdraws from the “sac” formed by the skin and thus the contact area with the substrate initially increases despite its volumetric recession. Furthermore, the oxide pins at the perimeter of the deflated “sac” on all the surfaces are tested, except for certain rough surfaces. With additional withdrawal of the liquid metal, the pinned angle gets smaller until eventually the oxide “sac” collapses. Thus, static contact angles can be manipulated mechanically from 0° to >140° due to hysteresis and are therefore uninformative. We also provide recommendations and best practices for wetting experiments, which may find use in applications that use these alloys such as soft electronics, composites, and microfluidics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Model for the Solid–Liquid Interfacial Free Energy at High Pressures

The free energy involved in the formation of an interface between two phases (e.g., a solid–liquid interface) is referred to as the interfacial free energy. For the case of solidification, the interfacial free energy dictates the height of the energy barrier required to nucleate stable clusters of the newly forming solid phase and is essential for producing an accurate solidification kinetics model using classical nucleation theory (CNT)-based methods. While various methods have been proposed for modeling the interfacial free energy for solid–liquid interfaces in prior literature, many of these formulations involve making restrictive assumptions or approximations, such as the system being at or near equilibrium (i.e., the system temperature is approximately equal to the melt temperature) or that the system is at pressures close to atmospheric. However, these approximations and assumptions may break down in highly non-equilibrium situations, such as in dynamic-compression experiments where metastable liquids that are undercooled by hundreds of kelvin or over-pressurized by several gigapascals or more are formed before eventually solidifying. We derive a solid–liquid interfacial free-energy model for such high-pressure conditions by considering the enthalpies of interactions between pairs of atoms or molecules. We also consider the contribution of interface roughness (disordering) by incorporating a multilayer interface model known as the Temkin n-layer model. Our formulation is applicable to a diverse variety of materials, and we demonstrate it by developing models specifically for two different materials: water and gallium. We apply our interfacial free-energy formulation to CNT-based kinetics simulations of several suites of dynamic-compression experiments that cause liquid water to solidify to the high-pressure solid polymorph ice VII and have found good agreement to the observed kinetics with only minor empirical fitting.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effects of Size and Shape on the Tolerances for Misalignment and Probabilities for Successful Oriented Attachment of Nanoparticles

Oriented attachment (OA) of nanoparticles is an important pathway of crystal growth, but tools for quantitatively modeling OA are lacking. Here we present several simple models that relate the probability of achieving OA to basic geometric parameters such as particle size, shape, and lattice periodicity. A Moiré-domain model is applied to understand twist-misorientations between parallel surfaces, and it predicts that the range of twist angles yielding perfect OA is inversely related to the width of the contact area. This is confirmed and further developed using a surface functional model, which predicts how crystallographic registration forces drive the emergence of complex orientational energy landscapes. The energy landscapes are predicted to possess local minima that can trap particles in imperfect alignments, and these local minima become deeper and more numerous as the contact area increases, making OA more challenging for large particles. Further, a second set of models is presented to understand the sequence of events by which two crystallographic faces become co-planer after collision. We use a ‘central force approximation’ to quantitatively predict the odds of attaining coalignment between various faces when particles collide with random misalignments, and we show that in the absence of biasing forces, the probability of attaining alignment on a given face is roughly proportional to its solid angle as viewed from the center of the particle. The model predicts that OA is most favorable between well-faceted particles and becomes exceedingly unlikely for large spherical particles that express many microfacets.

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

Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO 4 ) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO–salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO 4 . At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO 4 -doped PEOs, for both molecular weights. This work confirms that added salt causes a contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.

36 MATERIALS SCIENCE↗