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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Ion Exchange Technology Development in Support of the Urine Processor Assembly

The urine processor assembly (UPA) on the International Space Station (ISS) recovers water from urine via a vacuum distillation process. The distillation occurs in a rotating distillation assembly (DA) where the urine is heated and subjected to sub-ambient pressure. As water is removed, the original organics, salts, and minerals in the urine become more concentrated and result in urine brine. Eventually, water removal will concentrate the urine brine to super saturation of individual constituents, and precipitation occurs. Under typical UPA DA operating conditions, calcium sulfate or gypsum is the first chemical to precipitate in substantial quantity. During preflight testing with ground urine, the UPA achieved 85% water recovery without precipitation. However, on ISS, it is possible that crewmember urine can be significantly more concentrated relative to urine from ground donors. As a result, gypsum precipitated in the DA when operating at water recovery rates at or near 85%, causing the failure and subsequent re14 NASA Tech Briefs, September 2013 placement of the DA. Later investigations have demonstrated that an excess of calcium and sulfate will cause precipitation at water recovery rates greater than 70%. The source of the excess calcium is likely physiological in nature, via crewmembers' bone loss, while the excess sulfate is primarily due to the sulfuric acid component of the urine pretreatment. To prevent gypsum precipitation in the UPA, the Precipitation Prevention Project (PPP) team has focused on removing the calcium ion from pretreated urine, using ion exchange resins as calcium removal agents. The selectivity and effectiveness of ion exchange resins are determined by such factors as the mobility of the liquid phase through the polymer matrix, the density of functional groups, type of functional groups bound to the matrix, and the chemical characteristics of the liquid phase (pH, oxidation potential, and ionic strength). Previous experience with ion exchange resins has demonstrated that the most effective implementation for an ion exchange resin is a cartridge, or column, in which the resin is contained. Based on the results of equilibrium and sub-scale dynamic column testing, a possible solution for mitigating the calcium precipitation issue on the ISS has been identified. From an original pool of 13 ion exchange resins, two candidates have been identified that demonstrate substantial calcium removal on the sub-scale. The dramatic reduction in resin performance from published calcium uptake demonstrates the need for thorough evaluation of resins at the low pH and strong oxidizing environment present in the UPA. Chemical variations in the influent (calcium concentrations and pretreatment dosing) appear to have a noticeable impact on the calcium capacity of the resin. Low calcium concentrations and high pretreatment dosing will likely result in a decrease in calcium capacity. Conversely, low pre trea t - ment dosing will likely result in an increase in calcium capacity. In contrast, investigations at a variety of flow rates, length-to-diameter ratios, resin volumes, and flow regimes (continuous versus pulsed) show that changes in physical parameters do not have substantial impacts on resin performance in the very low specific velocity ranges of interest. This result is particularly useful because most commercial applications at higher specific velocities do show a relatively strong relationship between flow and capacity. The lack of a strong relationship will allow more flexibility in the implementation of an ion exchange bed for flight. Verification of subscale tests with flight-scale resin beds is recommended prior to implementation in the on-orbit UPA.

Mitchell, Julie↗
NASA NTRSDate not supplied

Broad Compatibility Study of Polymeric Materials with Ionic Silver Biocide, Part I

NASA is considering ionic silver as a residual biocide for use in potable water systems being planned for future exploration spacecraft. Compatibility of the biocide with the system’s wetted-materials of construction remains a challenge. Due to the relatively inert nature of plastics, their use in varied water system applications may offer unique opportunities to address many biocide compatibility issues. A 2020 ICES paper described a “Stage 1” assessment of several polymeric materials, in which coupons having a 2 cm 1 surface to volume ratio were exposed to solutions of 400 parts per billion (ppb) aqueous silver fluoride (AgF) for one week. In this current paper, additional Stage 1 test results are presented for select epoxies and lubricants applied on silver-inert substrates. The coupon exposure studies were also expanded to a duration of 5 weeks for the “well-behaved” Stage 1 plastics previously reported: those exhibiting silver losses above 10% and less than 50%. For this type of Stage 2 testing, silver biocide solution samples are taken from three separate (and not previously-sampled) coupon containers after 3 days, and 2, 3, 4, and 5 weeks of exposure. "Very well-behaved" Stage 1 plastics will be tested in the same manner over one year, with longer sample intervals; early-period results are included here. In addition, for select materials, the coupons were “aged” by refilling test containers with fresh AgF and observing the respective silver uptake over similar Stage 2 test durations. For all test series, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and ion-selective electrode (ISE) analyses were used to determine total and ionic silver (Ag+) concentrations, respectively. Additional sample analyses for Stage 2 tests includes total organic carbon (TOC), pH, conductivity, and oxidation-reduction potential (ORP). Ultimately, these early compatibility studies will be used to guide future material selections for developing silver biocide-compatible spacecraft water systems.

Silver Biocide↗
NASA NTRS1999

Determination of the Corrosive Conditions Present within Aircraft Lap-Splice Joints

The complexity of airframe structure lends itself to damage resulting from crevice corrosion. Fuselage lap-splice joints are a particularly important structural detail in this regard because of the difficulty associated with detection and measurement of corrosion in these occluded regions. The objective of this work is to develop a laboratory corrosion test protocol to identify the chemistry to which lap joints are exposed and to develop a model of the corrosion within the joints. A protocol for collecting and identifying the chemistry of airframe crevice corrosion has been developed. Capillary electrophoresis (CE) is used to identify the ionic species contained in corrosion product samples removed from fuselage lap splice joints. CE analysis has been performed on over sixty corrosion product samples removed from both civilian and military aircraft. Over twenty different ions have been detected. Measurements of pH of wetted corroded surfaces indicated an alkaline occluded solution. After determining the species present and their relative concentrations, the resultant solution was reproduced in bulk and electrochemical tests were performed to determine the corrosion rate. Electrochemical analyses of the behavior of AA2024-T3 in these solutions gave corrosion rates of up to 250 microns per year (10 mpy). Additional tests have determined the relative importance of each of the detected ions in model solutions used for future predictive tests. The statistically significant ions have been used to create a second generation solution. Laboratory studies have also included exposure tests involving artificial lap joints exposed to various simulated bulk and crevice environments. The extent and morphology of the attack in artificial lap joints has been compared to studies of corroded samples from actual aircraft. Other effects, such as temperature and potential, as well as the impact of the environment on fatigue crack growth have also been studied.

Lewis, Karen S.↗
NASA NTRS2002

Tetragonal Lysozyme, From Monomer to Crystal

The data now leads us to a comprehensive model for the process by which tetragonal lysozyme crystals are nucleated and subsequently grow. Lysozyme is typically desolubilized by addition of ionic salts. The salt anions bind to basic and other sites on the protein and promote protein-protein interactions, i.e., initiate the nucleation self assembly process. Formation of protein-protein interactions occurs at the expense of the protein-anion interactions, with the anions being released to the solution. The association follows a defined pattern, forming the "head to side" interactions of the crystal 4(3) helix. The presence of the high salt also promotes hydrophobic interactions between the protein molecules, further tightening their interaction. The solute assembly process persists after crystal nucleation, and the 4(3) helical structures form the subsequent growth units. AFM measurements show that the growth units follow the dimensions of these helices, and that those on the surface are more compact about the c-axis than in the bulk crystal, with adjacent helices riot being in contact. This further supports the role of hydrophobic interactions, as the surface is still in contact with the bulk solution. Once buried within the crystal the protein:salt ratio radically changes and the hydrophobic interactions relax to those measured crystallographically. Thus the crystal growth process recapitulates the initial stages of the nucleation process, and the two seamlessly merge. Experimental evidence, based upon face growth rate, AFM, and fluorescence energy transfer data, for a postulated model of the nucleation of tetragonal lysozyme crystals and how it transitions into crystal growth will be presented.

Pusey, Marc L.↗
NASA NTRSDate not supplied

Early Results from a Broad Compatibility Study of Various Materials with Ionic Silver Biocide

Ionic silver is baselined for microbial control in spacecraft potable water systems forfuture exploration missions, but materials compatibility analysis is required to evaluate thepassive depletion of ionic silver concentration onto wetted material surfaces over time.Various articles concerning such testing have been published that examine interactions withwater containing ionic silver biocide, but most tests have focused on only a couple ofmaterials each and comparing results of different evaluations to one another has provedchallenging.This paper reports the first results from static exposure testing of a large arrayof material coupons to a 400 parts per billion (ppb) aqueous silver fluoride (AgF) solution,using a surface to volume ratio of approximately 2 cm-1. The test is designed in two mainstages. Stage 1 is a one-week screening to evaluate silver uptake. Materials that performmodestly to well after that week are promoted to Stage 2, which is a longer test with periodicsampling to examine the silver uptake rates over time; these samples are evaluated for otherwater quality parameters in addition to the remaining silver concentration. In a tangentialinvestigation, select materials that take up some silver in Stage 1 may be “aged” by repeatingthe Stage 1 test to determine whether repeated exposure reduces silver uptake rate, andsuccessfully aged materials may then continue to Stage 2 testing. The materials under testinclude metallic and polymeric materials with various surface finishes, treatments, andcoatings, as well as select other materials historically used in spacecraft water systems. Thistest began in August 2019, and thus only includes early results; future follow-on papers willinclude additional results as the test progresses. The ultimate goal builds a broad, easilycomparable data set that can be used to guide material selections for silver biocide-compatible spacecraft water system design.

Silver Biocide↗
NASA NTRS1973

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Coplen, T. B.↗
NASA NTRS2002

Changes in the Molar Ellipticities of HEWL Observed by Circular Dichroism and Quantitated by Time Resolved Fluorescence Anisotropy Under Crystallizing Conditions

Fluid models for simple colloids predict that as the protein concentration is increased, crystallization should occur at some sufficiently high concentration regardless of the strength of attraction. However, empirical measurements do not fully support this assertion. Measurements of the second virial coefficient (B22) indicate that protein crystallization occurs only over a discrete range of solution parameters. Furthermore, observations of a strong correlation between protein solubility and B22, has led to an ongoing debate regarding the relationship between the two. Experimental work in our lab, using Hen Egg White Lysozyme (HEWL), previously revealed that the rotational anisotropy of the protein under crystallizing conditions changes systematically with pH, ionic strength and temperature. These observations are now supported by recent work revealing that small changes in the molar ellipticity also occur systematically with changes in ionic strength and temperature. This work demonstrates that under crystallization conditions, the protein native state is characterized by a conformational heterogeneity that may prove fundamental to the relationship between protein crystallization and protein solubility.

Sumida, John↗
NASA NTRSDate not supplied

Interpretable Machine Learning Models for Autonomous Characterization of Analogue Ocean World Seawater Chemistry and Biosignature Potential Using Isotope Ratio Data

Background: Future missions to ocean worlds, such as Enceladus and Europa, will attempt to characterize the subsurface seawater chemistry and assess the potential for life. Such missions will be equipped with capabilities to precisely measure volatile isotopes in plumes, atmospheres, and exospheres. Motivation: While large isotopic fractionations can indicate a biological source, there are signatures resulting from abiotic geochemical processes that mimic isotopic biosignatures. While machine learning (ML) has the potential to disentangle competing effects and biotic mimicry, high-dimensional isotope ratio mass spectrometry (IRMS) data is likely to contain noise/irrelevant features and involve complex statistical interactions that make human inference and interpretation difficult. Further, ML predictions with as far-reaching implications as an extraterrestrial biosignature on an ocean world requires the use of interpretable models (i.e., not “black box” models) with physically and mathematically meaningful feature spaces along with false positive diagnostics. Methods: We use volatile CO2 IRMS data of analogue ocean world seawaters to validate an ML approach to provide biogeochemical context for biosignature detection. We employ a feature selection method called nearest-neighbor projected distance regression (NPDR) that detects statistical interactions and helps elucidate the mechanisms of the Random Forest classification models. Results: We train and validate predictive ML models on volatile CO2 IRMS data of analogue ocean world seawaters to predict major salt components (e.g., MgSO4, NaHCO3), pH, ionic strength, and the presence of biosignatures. Features derived from IRMS measurements are augmented with extracted time-series features. Our results show high test accuracy and interpretability, which is increased by interaction network visualization, sample-wise variable importance scores, and single-sample class probability estimates. We demonstrate an ML mission software solution that triggers autonomous data transmission and biogeochemical sample prediction.

geochemistry↗
NASA NTRS1991

Self assembly properties of primitive organic compounds

A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic amphiphiles. One possibility is photochemical oxidation of hydrocarbons.

Deamer, D. W.↗
NASA NTRS1993

Transport methods and interactions for space radiations

This report presents a brief history leading to the involvement of the Langley Research Center of the National Aeronautics and Space Administration (NASA) in space-radiation physics and protection. Indeed, a relatively complete summary of technical capability as of the summer of 1990 is given. The Boltzmann equations for coupled ionic and neutronic fields are presented and inversion techniques for the Boltzmann operator are discussed. Errors generated by the straight ahead approximation are derived and are shown to be negligible for most problems of space-radiation protection. A decoupling of projectile propagation from the target fields greatly simplifies the Boltzmann equations and allows an analytic solution of the target fragment transport. Analytic and numerical methods of solving the projectile transport equations are discussed. The nuclear physics underlying the coefficients in the Boltzmann equation is discussed. A coupled-channel optical model is found as a consequence of the loose binding of nuclear matter and closure of the nuclear states in high-energy reactions. Transport solutions with the developed data base are used with laboratory experiments to validate both the transport code and the data base. Numerical benchmarks and comparison with Monte Carlo calculations are also used for code validation.

Wilson, John W.↗
NASA NTRS1973

The specification of distributed boundary conditions in numerical simulation of the ionosphere

The approach described makes it possible to use boundary conditions which do not have to be associated with any particular point of the solution interval. The approach was applied in a program which solves simultaneously the coupled differential equations describing the concentrations of the O(+) ions, their temperature, the electron temperature and the concentrations of O2(+), NO(+) and N2(+) ions. Several versions of the proposed scheme are described for various kinds of boundary conditions. Attention is given to a given columnar ionic content, a given incoming or outgoing flux, or a given height of the peak concentration.

Waldman, H.↗
NASA NTRS2003

Does the Iron K and Alpha: Line of Active Galactic Nuclei Arise from the Cerenkov Line-like Radiation?

When thermal relativistic electrons with isotropic distribution of velocities move in a gas region or impinge upon the surface of a cloud that consists of a dense gas or doped dusts, the Cerenkov effect produces peculiar atomic or ionic emission lines, which is known as the Cerenkov line - like radiation. This newly recognized emission mechanism may find wide applications in high-energy astrophysics. In this paper we tentatively adopt this new line emission mechanism to discuss the origin of the iron Kα feature of active galactic nuclei (AGNs). The motivation of this research is to attempt a solution to a problem encountered by the "disk fluorescence line" model, i.e. , the lack of temporal response of the observed iron Kα line flux to the changes of the X-ray continuum flux. If the Cerenkov line emission is indeed responsible significant ly for the iron Kα feature, the conventional scenario around the central supermassive black holes of AGNs would need to be modified to accomodate more energetic, more violent, and much denser environments than previously thought.

You, J. H.↗
NASA NTRS2020

Calorimetric Measurements of the Thermodynamic Properties of RE-Silicate Coating Materials

Thermodynamic quantities of coatings materials and siliceous debris-induced corrosion products are crucial to understand in order to develop mitigation strategies necessary to improve the durability of gas-turbine engines. Siliceous induced corrosion can occur when debris consisting mainly of CaO-MgO-Al2O3-SiO2 (CMAS) is ingested by aircraft engines during and after take-off, which sticks to hot surfaces and forms calcium rare-earth silicate oxyapatites. In this work, high-temperature oxide melt drop solution calorimetry (HT drop solution calorimetry) was used to obtain the enthalpies of formation for RE silicate (RE2Si2O7, RE2SiO5 where RE = Yb, Er, Y, Dy, Nd, Lu and Gd) environmental barrier coatings (EBCs) and the calcium RE silicate oxyapatite Ca2RE8(SiO4)6O2 (RE = Yb, Er, Y, Dy, Nd, Gd and Sm) corrosion products. Trends in the enthalpy of formation as a function of the ionic potential of the rare-earth cations in their related crystallographic sites are discussed.

Costa, Gustavo↗
NASA NTRS2000

Low potassium enhances sodium uptake in red-beet under moderate saline conditions

Due to the discrepancy in metabolic sodium (Na) requirements between plants and animals, cycling of Na between humans and plants is limited and critical to the proper functioning of bio-regenerative life support systems, being considered for long-term human habitats in space (e.g., Martian bases). This study was conducted to determine the effects of limited potassium (K) on growth, Na uptake, photosynthesis, ionic partitioning, and water relations of red-beet (Beta vulgaris L. ssp. vulgaris) under moderate Na-saline conditions. Two cultivars, Klein Bol, and Ruby Queen were grown for 42 days in a growth chamber using a re-circulating nutrient film technique where the supplied K levels were 5.0, 1.25, 0.25, and 0.10 mM in a modified half-strength Hoagland solution salinized with 50 mM NaCl. Reducing K levels from 5.0 to 0.10 mM quadrupled the Na uptake, and lamina Na levels reached -20 g kg-1 dwt. Lamina K levels decreased from -60 g kg-1 dwt at 5.0 mM K to -4.0 g kg-1 dwt at 0.10 mM K. Ruby Queen and Klein Bol responded differently to these changes in Na and K status. Klein Bol showed a linear decline in dry matter production with a decrease in available K, whereas for cv. Ruby Queen, growth was stimulated at 1.25 mM K and relatively insensitive to a further decreases of K down to 0.10 mM. Leaf glycinebetaine levels showed no significant response to the changing K treatments. Leaf relative water content and osmotic potential were significantly higher for both cultivars at low-K treatments. Leaf chlorophyll levels were significantly decreased at low-K treatments, but leaf photosynthetic rates showed no significant difference. No substantial changes were observed in the total cation concentration of plant tissues despite major shifts in the relative Na and K uptake at various K levels. Sodium accounted for 90% of the total cation uptake at the low K levels, and thus Na was likely replacing K in osmotic functions without negatively affecting the plant water status, or growth. Our results also suggest that cv. Ruby Queen can tolerate a much higher Na tissue concentration than cv. Klein Bol before there is any growth reduction. Grant numbers: 12180.

NASA Center KSC↗
NASA NTRS1999

Nutrient-substituted hydroxyapatites: synthesis and characterization

Incorporation of Mg, S, and plant-essential micronutrients into the structure of synthetic hydroxyapatite (HA) may be advantageous for closed-loop systems, such as will be required on Lunar and Martian outposts, because these apatites can be used as slow-release fertilizers. Our objective was to synthesize HA with Ca, P, Mg, S, Fe, Cu, Mn, Zn, Mo, B, and Cl incorporated into the structure, i.e., nutrient-substituted apatites. Hydroxyapatite, carbonate hydroxyapatite (CHA), nutrient-substituted hydroxyapatite (NHA), and nutrient-substituted carbonate hydroxyapatite (NCHA) were synthesized by precipitating from solution. Chemical and mineralogical analysis of precipitated samples indicated a considerable fraction of the added cations were incorporated into HA, without mineral impurities. Particle size of the HA was in the 1 to 40 nm range, and decreased with increased substitution of nutrient elements. The particle shape of HA was elongated in the c-direction in unsubstituted HA and NHA but more spherical in CHA and NCHA. The substitution of cations and anions in the HA structure was confirmed by the decrease of the d[002] spacing of HA with substitution of ions with an ionic radius less than that of Ca or P. The DTPA-extractable Cu ranged from 8 to 8429 mg kg-1, Zn ranged from 57 to 1279 mg kg-1, Fe from 211 to 2573 mg kg-1, and Mn from 190 to 1719 mg kg-1, depending on the substitution level of each element in HA. Nutrient-substituted HA has the potential to be used as a slow-release fertilizer to supply micronutrients, S, and Mg in addition to Ca and P.

NASA Discipline Life Support Systems↗
NASA NTRS1977

The effects of cations and anions on hydrogen chemisorption at Pt

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Huang, J. C.↗
NASA NTRS1971

Research on rechargeable oxygen electrodes

Studies were carried out on a number of factors which may influence the behavior of the platinum electrocatalyst of oxygen electrodes for use in rechargeable metal-oxygen batteries or hydrogen-oxygen fuel cells. The effects of pretreatments for various potentials and added ionic species, which could be present in such systems, were studied with reguard to: (1) the state of surface oxidation, (2) platinum dissolution, (3) the kinetics of oxygen evolution and reduction (including the role of hydrogen peroxide), and (4) changes in porous electrode structure. These studies were carried out on smooth platinum, platinized platinum, and Teflon-bonded platinum black electrodes in carefully purified electrolyte solutions. The main factors which appear to affect rechargeable oxygen electrode performance and life are: (1) the buildup of a refractory anodic layer on extended cycling, and (2) the dissolution of platinum.

Giner, J.↗
NASA NTRS1994

Equilibrium and Dynamics Properties of Poly(oxyethylene) Melts and Related Poly(alkylethers) from Simulations and Ab Initio Calculations

Molecular dynamics simulations of POE melts have been performed utilizing a potential force field parameterized to reproduce conformer energies and rotational energy barriers in dimethoxyethane as determined from ab initio electronic structure calculations. Chain conformations and dimensions of POE from the simulations were found to be in good agreement with predictions of a rotational isomeric state (RIS) model based upon the ab initio conformational. energies. The melt chains were found to be somewhat extended relative to chains at theta conditions. This effect will be discussed in light of neutron scattering experiments which indicate that POE chains are extended in the melt relative to theta solutions. The conformational characteristics of POE chains will also be compared with those of other poly (alkylethers), namely poly(oxymethylene), poly(oxytrimethylene) and poly(oxytetramethylene). Local conformational dynamics were found to be more rapid than in polymethylene. Calculated C-H vector correlation times were found to be in reasonable agreement with experimental values from C-13 NMR spin-lattice relaxation times. The influence of ionic salts on local conformations and dynamics will also be discussed.

Smith, Grant D.↗