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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Effect of solutes on the lattice parameters and elastic stiffness coefficients of body-centered tetragonal Fe

In this study, we compute changes in the lattice parameters and elastic stiffness coefficients C ij of body-centered tetragonal (bct) Fe due to Al, B, C, Cu, Mn, Si, and N solutes. Solute strain misfit tensors determine changes in the lattice parameters as well as strain contributions to the changes in the C ij . We also compute chemical contributions to the changes in the C ij , and show that the sum of the strain and chemical contributions agree with more computationally expensive direct calculations that simultaneously incorporate both contributions. Octahedral interstitial solutes, with C being the most important addition in steels, must be present to stabilize the bct phase over the body-centered cubic phase. We therefore compute the effects of interactions between interstitial C solutes and substitutional solutes on the bct lattice parameters and C ij for all possible solute configurations in the dilute limit, and thermally average the results to obtain effective changes in properties due to each solute. Finally, the computed data can be used to estimate solute-induced changes in mechanical properties such as strength and ductility, and can be directly incorporated into mesoscale simulations of multiphase steels to model solute effects on the bct martensite phase.

36 MATERIALS SCIENCE↗
DOE OSTI2015

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these two metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

New analytical solutions to the two-phase water faucet problem

Here, the one-dimensional water faucet problem is one of the classical benchmark problems originally proposed by Ransom to study the two-fluid two-phase flow model. With certain simplifications, such as massless gas phase and no wall and interfacial frictions, analytical solutions had been previously obtained for the transient liquid velocity and void fraction distribution. The water faucet problem and its analytical solutions have been widely used for the purposes of code assessment, benchmark and numerical verifications. In our previous study, the Ransom’s solutions were used for the mesh convergence study of a high-resolution spatial discretization scheme. It was found that, at the steady state, an anticipated second-order spatial accuracy could not be achieved, when compared to the existing Ransom’s analytical solutions. A further investigation showed that the existing analytical solutions do not actually satisfy the commonly used two-fluid single-pressure two-phase flow equations. In this work, we present a new set of analytical solutions of the water faucet problem at the steady state, considering the gas phase density’s effect on pressure distribution. This new set of analytical solutions are used for mesh convergence studies, from which anticipated second-order of accuracy is achieved for the 2nd order spatial discretization scheme. In addition, extended Ransom’s transient solutions for the gas phase velocity and pressure are derived, with the assumption of decoupled liquid and gas pressures. Numerical verifications on the extended Ransom’s solutions are also presented.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Relationships between Water’s Structure and Solute Affinity at Polypeptoid Brush Surfaces

Excellent antifouling surfaces are generally thought to create a tightly bound layer of water that resists solute adsorption, and highly hydrophilic surfaces such as those with zwitterionic functionalities are of significant current interest as antifoulant strategies. Furthermore, despite significant proofs-of-concept, we still lack a fundamental understanding of how the nanoscopic structure of this hydration layer translates to reduced fouling, how surface chemistry can be tuned to achieve antifouling through hydration water, and why, in particular, zwitterionic surfaces seem so promising. Here, we use molecular dynamics simulations and free energy calculations to investigate the molecular relationships among surface chemistry, hydration water structure, and surface–solute affinity across a variety of surface-decorated chemistries. Specifically, we consider polypeptoid-decorated surfaces that display well-known experimental antifouling capabilities and that can be synthesized sequence specifically, with precise backbone positioning of, e.g., charged groups. Through simulations, we calculate the affinities of a range of small solutes to polypeptoid brush surfaces of varied side-chain chemistries. We then demonstrate that measures of the structure of surface hydration water in response to a particular surface chemistry signal solute–surface affinity; specifically, we find that zwitterionic chemistries produce solute–surface repulsion through highly coordinated hydration water while suppressing tetrahedral structuring around the solute, in contrast to uncharged surfaces that show solute–surface affinity. Based on the relationship of this structural perturbation to the affinity of small-molecule solutes, we propose a molecular mechanism by which zwitterionic surface chemistries enhance solute repulsion, with broader implications for the design of antifouling surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Exact solitary solution of Schamel equation in plasmas with negative ions

A theoretical investigation is carried out for understanding the properties of the solitary solution in plasmas with negative ions. Schamel equation for a plasma consisting of electron, positive ions and negative ions has been derived by using the reductive perturbation method. The effects of negative ions and the density on the properties of the solitary solution is discussed. We make use of the extended mapping method and auxiliary equation to obtain the solution of Schamel equation. This solution includes the Jacobi elliptic function solutions, hyperbolic function solutions, rational solutions, and periodic wave solutions. Furthermore, we show that the incorporate negative ion effects in the nonlinear propagation of ion acoustic waves that are controlled by trapped electrons and the results of the solitary solution in plasmas with negative ions model are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

About simple nonlinear and linear superpositions of special exact solutions of Veselov-Novikov equation

New exact solutions, nonstationary and stationary, of Veselov-Novikov (VN) equation in the forms of simple nonlinear and linear superpositions of arbitrary number N of exact special solutions u{sup (n)}, n= 1, Horizontal-Ellipsis , N are constructed via Zakharov and Manakov {partial_derivative}-dressing method. Simple nonlinear superpositions are represented up to a constant by the sums of solutions u{sup (n)} and calculated by {partial_derivative}-dressing on nonzero energy level of the first auxiliary linear problem, i.e., 2D stationary Schroedinger equation. It is remarkable that in the zero energy limit simple nonlinear superpositions convert to linear ones in the form of the sums of special solutions u{sup (n)}. It is shown that the sums u=u{sup (k{sub 1})}+...+u{sup (k{sub m})}, 1 Less-Than-Or-Slanted-Equal-To k{sub 1} < k{sub 2} < Horizontal-Ellipsis < k{sub m} Less-Than-Or-Slanted-Equal-To N of arbitrary subsets of these solutions are also exact solutions of VN equation. The presented exact solutions include as superpositions of special line solitons and also superpositions of plane wave type singular periodic solutions. By construction these exact solutions represent also new exact transparent potentials of 2D stationary Schroedinger equation and can serve as model potentials for electrons in planar structures of modern electronics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Electronic origin of strain effects on solute stabilities in iron

Nonuniform strain fields might induce the segregation of alloying solutes and ultimately lead to the mechanical performance degradation of body-centered-cubic (bcc) Fe based steels serving in extreme environments, which is worthy of investigation. In this paper, two typical volume-conserving strains, shear strain (SS) and normal strain (NS), are proposed to investigate the strain effects on solute stabilities in bcc iron by first-principles calculations. For solutes in each transition metal group, the calculated substitution energy change due to SS exhibits a linear dependence on the valence d radius of the solutes, and the slope decreases in an exponential manner as a function of the absolute difference between the Watson's electronegativity of iron and the averaged value of each transition metal group. This regularity is attributed to the Pauli repulsion between the solutes and the nearest neighboring Fe ions modulated by the hybridization of valence d bands and concluded to be originated from the characteristics of valence d bonding between the transition-metal solutes and Fe ions under SS. For main-group and post transition-metal solutes, the considerable drop of substitution energy change due to NS is concluded to be originated from the low-energy side shift of the widened valence s and p bands of the solutes. Our results indicate that the stabilities of substitutional solutes in iron under volume-conserving strain directly correlate with the intrinsic properties of the alloying elements, such as the valence d radius and occupancy, having or not having valence s and p bands.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Classical string solutions in AdS{sub 5}xS{sup 5}

We discuss some new simple closed bosonic string solutions in AdS{sub 5}xS{sup 5} that may be of interest in the context of AdS/CFT duality. In the first part of this work we consider solutions with two spins (S{sub 1},S{sub 2}) in AdS{sub 5}. Starting from the flat-space solutions and using perturbation theory in the curvature of AdS{sub 5} space, we construct leading terms in the small two-spin solution. We find corrections to the leading Regge term in the classical string energy and uncover a discontinuity in the spectrum for a certain type of solution. We then analyze the connection between small-spin and large-spin limits of string solutions in AdS{sub 5}. We show that the S{sub 1}=S{sub 2} solution in AdS{sub 5} found in earlier papers admits both limits only in the simplest cases of the folded and rigid circular strings. In the second part of the paper, we construct a new class of chiral solutions in R{sub t}xS{sup 5} for which embedding coordinates of S{sup 5} satisfy the linear Laplace equations. They generalize the previously studied rigid string solutions. We study in detail a simple nontrivial example.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Type D solutions of 3D new massive gravity

In a recent reformulation of three-dimensional new massive gravity, the field equations of the theory consist of a massive (tensorial) Klein-Gordon type equation with a curvature-squared source term and a constraint equation. Using this framework, we present all algebraic type D solutions of new massive gravity with constant and nonconstant scalar curvatures. For constant scalar curvature, they include homogeneous anisotropic solutions which encompass both solutions originating from topologically massive gravity, Bianchi types II, VIII, IX, and those of non-topologically massive gravity origin, Bianchi types VI{sub 0} and VII{sub 0}. For a special relation between the cosmological and mass parameters, {lambda}=m{sup 2}, they also include conformally flat solutions, and, in particular, those being locally isometric to the previously-known Kaluza-Klein type AdS{sub 2}xS{sup 1} or dS{sub 2}xS{sup 1} solutions. For nonconstant scalar curvature, all the solutions are conformally flat and exist only for {lambda}=m{sup 2}. We find two general metrics which possess at least one Killing vector and comprise all such solutions. We also discuss some properties of these solutions, delineating among them black hole type solutions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2014

SCM Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership

This report summarizes experimental work performed by SIMCO Technologies Inc. (SIMCO) as part of the Cementitious Barriers Partnership (CBP) project. The test series followed an experimental program dedicated to the study of ordinary Portland cement (OPC) hydrated cement pastes exposed to aggressive solutions. In the present study, the scope is extended to hydrated cement pastes incorporating supplementary cementitious materials (SCM) such as fly ash and ground granulated blast furnace slag (GGBFS). Also, the range of aggressive contact solutions was expanded. The experimental program aimed at testing aggressive contact solutions that more closely mimic the chemical composition of saltstone pore solution. Five different solutions, some of which incorporated high levels of carbonate and nitrate, were placed in contact with four different hydrated cement paste mixes. In all solutions, 150 mmol/L of SO 4 2– (14 400 ppm) were present. The solutions included different pH conditions and different sodium content. Two paste mixes were equivalent to Vault 1/4 and Vault 2 concrete mixes used at SRS in storage structures. Two additional paste mixes, cast at the same water-to-cement ratio and using the same cements but without SCMs, were also tested. The damage evolution in samples was monitored using ultrasonic pulse velocity (UPV) and mass measurements. After three and twelve months of exposure conditions, samples were taken out of solution containers and analyzed to perform migration tests and porosity measurements. Globally, results were in line with the previous study and confirmed that high pH may limit the formation of some deleterious phases like gypsum. In this case, ettringite may form but is not necessarily associated with damage. However, the high concentration of sodium may be associated with the formation of an AFm-like mineral called U-phase. The most significant evidences of damage were all associated with the Vault 2 paste analog. This material proved very sensitive to high pH. All measurement techniques used to monitor and evaluate damage to samples indicated significant alterations to this mix when immersed in contact solutions containing sodium hydroxide. It was hypothesized that the low cement content, combined with high silica content coming from silica fume, fly ash and GGBFS led to the presence unreacted silica. It is possible that the pozzolanic reaction of these SCMs could not be activated due to the low alkali content, a direct consequence of low cement content. In this scenario, the material end up having a lot of silica available to react upon contact with sodium hydroxide, possibly forming a gel that may be similar to the gel formed in alkali-silica reactions. This scenario needs further experimental confirmation, but it may well explain the poor behavior of mix PV2 in presence of NaOH.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

An Investigation into Solution Verification for CFD-DEM

This report presents the study of the convergence behavior of the computational fluid dynamicsdiscrete element method (CFD-DEM) method, specifically National Energy Technology Laboratory’s (NETL) open source MFiX code (MFiX-DEM) with a diffusion based particle-tocontinuum filtering scheme. In particular, this study focused on determining if the numerical method had a solution in the high-resolution limit where the grid size is smaller than the particle size. To address this uncertainty, fixed particle beds of two primary configurations were studied: i) fictitious beds where the particles are seeded with a random particle generator, and ii) instantaneous snapshots from a transient simulation of an experimentally relevant problem. Both problems considered a uniform inlet boundary and a pressure outflow. The CFD grid was refined from a few particle diameters down to 1/6 th of a particle diameter. The pressure drop between two vertical elevations, averaged across the bed cross-section was considered as the system response quantity of interest. A least-squares regression method was used to extrapolate the grid-dependent results to an approximate “grid-free” solution in the limit of infinite resolution. The results show that the diffusion based scheme does yield a converging solution. However, the convergence is more complicated than encountered in simpler, single-phase flow problems showing strong oscillations and, at times, oscillations superimposed on top of globally non-monotonic behavior. The challenging convergence behavior highlights the importance of using at least four grid resolutions in solution verification problems so that (over-determined) regression-based extrapolation methods may be applied to approximate the grid-free solution. The grid-free solution is very important in solution verification and VVUQ exercise in general as the difference between it and the reference solution largely determines the numerical uncertainty. By testing different randomized particle configurations of the same general problem (for the fictitious case) or different instances of freezing a transient simulation, the numerical uncertainties appeared to be on the same order of magnitude as ensemble or time averaging uncertainties. By testing different drag laws, almost all cases studied show that model form uncertainty in this one, very important closure relation was larger than the numerical uncertainty, at least with a reasonable CFD grid, roughly five particle diameters. In this study, the diffusion width (filtering length scale) was mostly set at a constant of six particle diameters. A few exploratory tests were performed to show that similar convergence behavior was observed for diffusion widths greater than approximately two particle diameters. However, this subject was not investigated in great detail because determining an appropriate filter size is really a validation question which must be determined by comparison to experimental or highly accurate numerical data. Future studies are being considered targeting solution verification of transient simulations as well as validation of the filter size with direct numerical simulation data.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2017

Unraveling the Solution‐State Supramolecular Structures of Donor–Acceptor Polymers and their Influence on Solid‐State Morphology and Charge‐Transport Properties

Abstract Polymer self‐assembly in solution prior to film fabrication makes solution‐state structures critical for their solid‐state packing and optoelectronic properties. However, unraveling the solution‐state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution‐state structure and the charge‐transport properties in field‐effect transistors. Here, for the first time, it is revealed that the thin‐film morphology of a conjugated polymer inherits the features of its solution‐state supramolecular structures. A “solution‐state supramolecular structure control” strategy is proposed to increase the electron mobility of a benzodifurandione‐based oligo( p‐ phenylene vinylene) (BDOPV)‐based polymer. It is shown that the solution‐state structures of the BDOPV‐based conjugated polymer can be tuned such that it forms a 1D rod‐like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution‐state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V −1 s −1 . This work demonstrates that “solution‐state supramolecular structure” control is critical for understanding and optimization of the thin‐film morphology and charge‐transport properties of conjugated polymers.

Zheng, Yu‐Qing↗
DOE OSTI2011

The Effect of Crystallizing and Non-crystallizing Cosolutes on Succinate Buffer Crystallization and the Consequent pH Shift in Frozen Solutions

To effectively inhibit succinate buffer crystallization and the consequent pH changes in frozen solutions. Using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD), the crystallization behavior of succinate buffer in the presence of either (i) a crystallizing (glycine, mannitol, trehalose) or (ii) a non-crystallizing cosolute (sucrose) was evaluated. Aqueous succinate buffer solutions, 50 or 200 mM, at pH values 4.0 or 6.0 were cooled from room temperature to -25 C at 0.5 C/min. The pH of the solution was measured as a function of temperature using a probe designed to function at low temperatures. The final lyophiles prepared from these solutions were characterized using synchrotron radiation. When the succinic acid solution buffered to pH 4.0, in the absence of a cosolute, was cooled, there was a pronounced shift in the freeze-concentrate pH. Glycine and mannitol, which have a tendency to crystallize in frozen solutions, remained amorphous when the initial pH was 6.0. Under this condition, they also inhibited buffer crystallization and prevented pH change. At pH 4.0 (50 mM initial concentration), glycine and mannitol crystallized and did not prevent pH change in frozen solutions. While sucrose, a non-crystallizing cosolute, did not completely prevent buffer crystallization, the extent of crystallization was reduced. Sucrose decomposition, based on XRD peaks attributable to {beta}-D-glucose, was observed in frozen buffer solutions with an initial pH of 4.0. Trehalose completely inhibited crystallization of the buffer components when the initial pH was 6.0 but not at pH 4.0. At the lower pH, the crystallization of both trehalose dihydrate and buffer components was evident. When retained amorphous, sucrose and trehalose effectively inhibited succinate buffer component crystallization and the consequent pH shift. However, when trehalose crystallized or sucrose degraded to yield a crystalline decomposition product, crystallization of buffer was observed. Similarly, glycine and mannitol, two widely used bulking agents, inhibited buffer component crystallization only when retained amorphous. In addition to stabilizing the active pharmaceutical ingredient, lyoprotectants may prevent solution pH shift by inhibiting buffer crystallization.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Fluorescent solute-partitioning characterization of layered soft contact lenses

Partitioning of aqueous packaging, wetting, and care-solution agents into and out of soft contact lenses (SCLs) is important for improving wear comfort and also for characterizing lens physico-chemical properties. We illustrate both features of partitioning by application of fluorescent-solute partitioning into DAILIES TOTAL1® (delefilcon A) water-gradient SCLs, which exhibit a layered structure of a silicone-hydrogel (SiHy) core sandwiched between thin surface-gel layers. Two-photon fluorescence confocal laser-scanning microscopy and attenuated total-reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) characterize the lens and assess uptake profiles of six prototypical fluorescent solutes. Comparison of solute uptake in a SiHy-core prototype lens (i.e., O 2 OPTIX™) validates the core SiHy structure of DAILIESTOTAL1®. To establish surface-layer charge, partition coefficients and water contents are obtained for aqueous pH values of 4 and 7.4. Solute fluorescence-intensity profiles clearly confirm a layered structure for the DAILIES TOTAL1® lenses. In all cases, aqueous solute partition coefficients are greater in the surface layers than in the SiHy core, signifying higher water in the surface gels. ATR-FTIR confirms surface-layer mass water contents of 82 ± 3%. Water uptake and hydrophilic-solute uptake at pH 4 compared with that at pH 7.4 reveal that the surface-gel layers are anionic at physiologic pH 7.4, whereas both the SiHy core and O 2 OPTIX™ (lotrafilcon B) are nonionic. Here, we successfully confirm the layered structure of DAILIES TOTAL1®, consisting of an 80-μm-thick SiHy core surrounded by 10-μm-thick polyelectrolyte surface-gel layers of significantly greater water content and aqueous solute uptake compared with the core. Accordingly, fluorescent-solute partitioning in SCLs provides information on gel structure and composition, in addition to quantifying uptake and release amounts and rates.

Attenuated total-reflectance Fourier-transform inf↗
DOE OSTI2023

Using high pressure solutions of polyfluoroacrylate and CO 2 to Seal cement cracks for improved wellbore integrity

Polyfluoroacrylate (PFA) is a hydrophobic and oleophobic polymer that is soluble in high pressure carbon dioxide (CO 2 ). In this study, the ability of PFA-CO 2 solutions to greatly reduce the apparent permeability of split or cracked Portland cement cylindrical samples is assessed. The apparent permeability values of confined samples were determined before and after treatment with PFA-CO 2 solutions. In four tests, PFA-CO 2 solutions were continuously displacing pure CO 2 from the cracked cement and the decrease in apparent permeability due to PFA adsorption and wettability alteration was monitored. The lowest apparent permeability cracked cement sample (81 nD) was completely sealed with a very small amount of solution. Samples with initial apparent permeabilities of 89 μD and 29.4 mD exhibited 92% and 99% reductions in permeability, respectively, before the experiments had to be stopped because of the excessively large increase in pressure drop. A 50% reduction in apparent permeability was observed with a 3.80 mD sample. Four other split cement samples (bound together with tape) with an initial apparent permeability in the 9.0–70 mD range were removed from the core holder and immersed in a PFA-CO 2 solution for 24 h to allow for PFA adsorption. Then the PFA-CO 2 solution was depressurized, allowing for the deposition of additional PFA from the solution within the crack as the pressure fell below the cloud point pressure of the PFA-CO 2 solution. These four samples were then confined again in a core holder and apparent permeability reductions of 29–93% were observed. Finally, results from these eight experiments indicates that the more substantial reductions in the nD – mD apparent permeability of the cracked cement correlated to lower initial crack permeability, higher PFA concentration, and slower injection rate of the PFA-CO 2 solution into the crack.

58 GEOSCIENCES↗
DOE OSTI2017

Surface defects on the Gd{sub 2}Zr{sub 2}O{sub 7} oxide films grown on textured NiW technical substrates by chemical solution method

Epitaxial growth of oxide thin films has attracted much interest because of their broad applications in various fields. In this study, we investigated the microstructure of textured Gd{sub 2}Zr{sub 2}O{sub 7} films grown on (001)〈100〉 orientated NiW alloy substrates by a chemical solution deposition (CSD) method. The aging effect of precursor solution on defect formation was thoroughly investigated. A slight difference was observed between the as-obtained and aged precursor solutions with respect to the phase purity and global texture of films prepared using these solutions. However, the surface morphologies are different, i.e., some regular-shaped regions (mainly hexagonal or dodecagonal) were observed on the film prepared using the as-obtained precursor, whereas the film prepared using the aged precursor exhibits a homogeneous structure. Electron backscatter diffraction and scanning electron microscopy analyses showed that the Gd{sub 2}Zr{sub 2}O{sub 7} grains present within the regular-shaped regions are polycrystalline, whereas those present in the surrounding are epitaxial. Some polycrystalline regions ranging from several micrometers to several tens of micrometers grew across the NiW grain boundaries underneath. To understand this phenomenon, the properties of the precursors and corresponding xerogel were studied by Fourier transform infrared spectroscopy and coupled thermogravimetry/differential thermal analysis. The results showed that both the solutions mainly contain small Gd−Zr−O clusters obtained by the reaction of zirconium acetylacetonate with propionic acid during the precursor synthesis. The regular-shaped regions were probably formed by large Gd−Zr−O frameworks with a metastable structure in the solution with limited aging time. This study demonstrates the importance of the precise control of chemical reaction path to enhance the stability and homogeneity of the precursors of the CSD route. - Highlights: •We investigate microstructure of Gd{sub 2}Zr{sub 2}O{sub 7} films grown by a chemical solution route. •The aging effect of precursor solution on formation of surface defect was thoroughly studied. •Gd−Zr−O clusters are present in the precursor solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The apparent reversal of the Law of Mass Action in concentrated multicomponent aqueous solutions

Although it is well known that aqueous electrolyte solutions behave non-ideally, few are so non-ideal that adding an electrolyte to a saturated solution with a common ion enhances rather than depresses solubility. Nonetheless, this apparent reversal of the Law of Mass Action (LMA) has been observed in simple nitrate solutions at high concentrations. A leading hypothesis is that ion clusters are formed and stabilized by ions having different charge densities. We report the present study examines this concept, in part by reviewing relevant data from multicomponent aqueous solutions containing sodium nitrate (NaNO 3 ), sodium nitrite (NaNO 2 ), sodium hydroxide (NaOH), and sodium aluminate (NaAl(OH) 4 ) - the major constituents in alkaline nuclear waste. Here, NaOH and NaAl(OH) 4 did not enhance the solubility of NaNO 3 or NaNO 2 , whereas NaNO 2 and NaNO 3 enhanced rather than depressed the solubility of each other despite each having the sodium cation (Na + ) in common. Solutions evaluated in this study have more than 20 molal total Na + concentration, and most have less than one mole of water per mole of ion. Thus, this reversal of the LMA occurs in solutions where there is not enough water to fully hydrate the ions, pointing to the importance of ion cluster formation. Within the composition range of the solutions analyzed here, this reversal of the LMA occurs regardless of NaAl(OH) 4 and NaOH concentrations. Elevated temperatures also result in the reversal of the LMA in the subsystems NaNO 2 -NaNO 3 -H 2 O and NaOH-NaNO 3 -H 2 O, consistent with spectroscopic and computational studies showing enhanced interactions at higher temperatures. Although speciation in these highly concentrated electrolyte solutions is not well understood, the stabilization of ion clusters by: (i) optimizing charge density around the ions through different combinations of mixed cations and anions in solution; and (ii) high temperatures where ions experience prolonged contact, offers important clues for future research into how these species control solubility.

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

Effect of electrode rinse solutions on the electrodialysis of concentrated salts

The data presented indicate that modest attention to the chemistry of the electrode rinse solution can yield as much as 56% improvement in process efficiency. When operating electrodialysis (ED) with salt concentrations greater than 10,000 mg/l (as NaCl) the amperage can be relatively high even at low voltages. To maximize the overall rate of ion transport from diluate to concentrate, there is a need to minimize resistances in the electrode cells since these can represent as much as 30% of the total resistances in the entire process and in this particular ED unit, represented resistance roughly equivalent to that within the membrane stack. This work describes the performance of a 10-cell pair, 200 cm 2 (0.02 m 2 ) per membrane, pilot ED unit operated in batch mode at 5 V potential. The feedstock to the stack was varied from 0.5% to 6% NaCl. Results from Volt-amp profiles (2.0–15 V) were used as the rationale for choosing the preferred electrode rinse solution, 90 g/l (kg/m 3 ) disodium sulfate at pH 12.5. The recommended solution of 30 g/l (kg/m 3 ) disodium sulfate at neutral pH was tested against stronger solutions (60, 90, and 120 g/l (kg/m 3 ) disodium sulfate) at neutral pH and with 1 g/l (kg/m 3 ) sodium hydroxide added to yield solutions at pH 12.5. There were stark differences in the performance of the ED unit between the solutions at pH 7 and those at pH 12.5. The slopes of the Volt-amp profiles improved indicating less resistance to ion flow at pH 12.5. Most of the difference can be attributed to the greater conductivity of sodium hydroxide compared to disodium sulfate, where even a modest addition of 1 g/l (kg/m 3 ) sodium hydroxide increased the conductivity of the solution between 8 and 20% depending on the concentration of disodium sulfate. Most notably, the initiation voltage was 2.39 ± 0.08 V with solutions at pH 7 and 1.99 V ± 0.04 V when the rinse solutions were around pH 12.5, a difference of around 0.42 V. Since the full batch runs were performed at 5.0 V, this 0.42 V differential represented a loss of 8% in process efficiency. A series of tests showed a shift in initiation voltage occurred between pH 11.5 and 12.5. Nernst equations for water electrolysis are coupled with a simple flux model that estimates the concentration of hydroxide and hydronium ions at the electrode surfaces. This model indicates that the potential demanded by the electrodes is directly linked to the current. Furthermore, there is a steep drop in the potential demanded by the anode when there is sufficient hydroxide available to generate oxygen from hydroxide as opposed to generation from water. The voltage demand is minimal at pH 12.5 and reflective of the reference standard voltage (just over 1.23 V predicted at 0.1 amps). However, the flux model predicts that the voltage demanded by the electrodes at pH 7 is 1.61 V at 0.1 amps (the lowest amperage measurable with the power pack). In conclusion, comparing this result to the reference standard (E 0 = -1.23 V) yields a satisfactory explanation for the observed difference below reference standard of 0.42 V.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗