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DOE OSTI2021

Synergistic Coupling of CO2 and H2O during Expansion of Clays in Supercritical CO2-CH4 Fluid Mixtures

A combination of in operando IR and XRD methods were used to investigate the interaction of variably hydrated supercritical CO2-CH4 fluids with Na/NH4/Cs substituted montmorillonites. Comparing the behavior of Na-clay exposed to CH4 versus CO2 dominant fluid phases demonstrated that CO2 disrupts the H-bond network of intercalated H2O. At relatively low potentials of H2O, CO2 facilitates H2O intercalation and expansion of the interlayer region of the Na-clay. In contrast, CO2 inhibited H2O intercalation but promoted expansion of the Cs-clay. The NH4-clay displayed intermediated behavior. Methane likely intercalated the clays but opportunistically, filling unoccupied space after CO2 and H2O actively expanded the interlayer region. By comparing and contrasting the behavior of the Cs and NH4 clays to the Na Clay we conclude that, whereas H2O is required for initial Na-clay expansion, CO2 synergistically facilitated expansion and hydration of Na-clay by mixing with H2O (the entropic contribution) and participating in the outer solvation sphere of Na (the enthalpic contribution). In contrast, CO2 can directly solvate interlayer Cs and NH4 and cause expansion in the absence of H2O; nonetheless, H2O and CO2 also act synergistically to facilitate expansion of the Cs and NH4 clays at low H2O concentrations.

Loring, John S.↗

DOE OSTI2015

Synthesis, Structure, and Rigid Unit Mode-like Anisotropic Thermal Expansion of BaIr 2 In 9

This Article reports the synthesis of large single crystals of BaIr 2 In 9 using In flux and their characterization by variable-temperature single-crystal and synchrotron powder X-ray diffraction, resistivity, and magnetization measurements. The title compound adopts the BaFe 2 Al 9 -type structure in the space group P6/mmm with room temperature unit cell parameters a = 8.8548(6) angstrom and c = 4.2696(4) A. BaIr 2 In 9 exhibits anisotropic thermal expansion behavior with linear expansion along the c axis more than 3 times larger than expansion in the ab plane between 90 and 400 K. This anisotropic expansion originates from a rigid unit mode-like mechanism similar to the mechanism of zero and negative thermal expansion observed in many anomalous thermal expansion materials such as ZrW 2 O 8 and ScF 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Tunable Thermal Expansion from Negative, Zero, to Positive in Cubic Prussian Blue Analogues of GaFe(CN) 6

The control of thermal expansion of open framework Prussian blue analogues is vital but remains challenging. The present work proposes an effective method to control the thermal expansion, in which guest ions (Na + ) and molecules (H 2 O) can adjust the coeffecient of thermal expansion from strong negative, to near zero, to positive in GaFe(CN) 6 Prussian blue analogues. Direct experimental evidence by high resolution synchrotron X-ray diffraction and X-ray absorption fine structure shows that the guest ions or molecules have intense dampening effect on the transverse vibrations of -Ga–N≡C–Fe– linkage responsible for NTE, especially for N atoms. The role of guests in controlling thermal expansion is attributed to the strong interaction of local environment – steric dampening. Furthermore, the present study demonstrates that electrochemical or redox intercalation of guest ions can be a general and effective method for controlling thermal expansion for those open framework materials with negative thermal expansion driven by low Frequency phonons.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Uncertainty Quantification in CO 2 Sequestration Using Surrogate Models from Polynomial Chaos Expansion

In this paper, surrogate models are iteratively built using polynomial chaos expansion (PCE) and detailed numerical simulations of a carbon sequestration system. Output variables from a numerical simulator are approximated as polynomial functions of uncertain parameters. Once generated, PCE representations can be used in place of the numerical simulator and often decrease simulation times by several orders of magnitude. However, PCE models are expensive to derive unless the number of terms in the expansion is moderate, which requires a relatively small number of uncertain variables and a low degree of expansion. To cope with this limitation, instead of using a classical full expansion at each step of an iterative PCE construction method, we introduce a mixed-integer programming (MIP) formulation to identify the best subset of basis terms in the expansion. This approach makes it possible to keep the number of terms small in the expansion. Monte Carlo (MC) simulation is then performed by substituting the values of the uncertain parameters into the closed-form polynomial functions. Based on the results of MC simulation, the uncertainties of injecting CO{sub 2} underground are quantified for a saline aquifer. Moreover, based on the PCE model, we formulate an optimization problem to determine the optimal CO{sub 2} injection rate so as to maximize the gas saturation (residual trapping) during injection, and thereby minimize the chance of leakage.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Controllable thermal expansion and magnetic structure in Er 2 (Fe,Co) 14 B intermetallic compounds

The control of thermal expansion is attractive but remains challenging for the studies of negative thermal expansion materials. Here, we report a continuously controllable thermal expansion from negative to positive by means of adjusting the magnetic moment of Fe in Er 2 (Fe,Co) 14 B intermetallic compounds. Interestingly, a zero thermal expansion (ZTE) has been achieved in a wide temperature range (ΔT = 355 K), which is larger than most existing ZTE alloys. The spontaneous magnetostriction (ω S ) reveals a negative contribution arising from the magneto-volume effect to the controllable thermal expansion. The present study could be suitable for the design of controllable thermal expansion of other alloys related to the magneto-volume effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Negative thermal expansion and the role of hybridization in perovskite-type PbTiO 3 -Bi(Cu 0.5 Ti 0.5) O 3

PbTiO 3 -BiMeO 3 ferroelectrics have attracted much attention due to not only their extremely large polarization and piezoelectricity but also their controllable thermal expansion. In this study, we present a new binary system of (1 - x)PbTiO 3 -xBi(Cu 0.5 Ti 0.5 )O 3 possessing large tetragonality and enhanced spontaneous polarization. Interestingly, a combination of near zero thermal expansion and negative thermal expansion over a temperature range of RT to T C (~550 °C) has been observed in tetragonal 0.85PbTiO 3 -0.15Bi(Cu 0.5 Ti 0.5 )O 3 . The comprehensive structure analysis addressed that the abnormal thermal expansion is coupled to the spontaneous volume ferroelectrostriction. Moreover, the chemical bonding investigation by a maximum entropy method further attests that the covalent hybridization of Pb/Bi–O bonds plays a vital role in the improved ferroelectricity and interacts with thermal vibration to dominate the crossover from positive to negative thermal expansion. fINALLY, The present studies would give direct evidence to verify the theoretical calculations and could be extended to reveal the nature of thermal expansion in ferroelectrics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Baryon Effective Theories and Phenomenology in the 1/ N C Expansion

Chiral perturbation theory (ChPT) and the 1/ N C expansion provide systematic frameworks to investigate the strong interaction at low energy. There are two main focuses of this dissertation. First, analyzing the masses of baryons in the framework of the 1/ N C expansion, using the available physical masses and masses calculated in lattice QCD. Second, combining both ChPT and the 1/ N C expansion into a single framework and applying it to the phenomenology of baryons with three light-quark flavors. In the first focus, the baryon states are organized into irreducible representations of SU(6)×O(3), where the [56,&ell; P = 0 + ] contains the ground state and radially excited baryons, and the [56,2 + ] and [70,1 - ] contain orbitally excited states are analyzed. The analyses are carried out to O(1/ N C ) and first order in the quark masses. The issue of state identifications is discussed. Numerous parameter independent mass relations and the famous Gell-Mann-Okubo (GMO) and Equal-Spacing (ES) relations are tested. Also, the quark mass dependence of the operator coefficients for baryon mass is discussed. In the second focus, a small scale expansion of the combined approach is defined as the ξ-expansion, in which the power counting of 1/ N C and chiral expansions are linked as O(p) = O(1/ N C ) = O(ξ). A calculation of one-loop corrections to the ground state baryon masses, vector and axial-vector currents up to O(x&i; 3 ) is presented. Moreover, the physical and lattice QCD masses are considered in order to understand the quark mass dependence, along with an analysis of the violations to GMO, ES and Gürsey-Radicati (GR) mass relations, and their dependence on N C .

Fernando, Madappuli Arachchige Ishara↗

DOE OSTI2022

High Throughput Coefficient Thermal Expansion Testing Utilizing Digital Image Correlation

Dr. Fitzgerald, a postdoc at Sandia National Laboratories, works in a materials of mechanics group characterizing material properties of ductile materials. Her presentation focuses specifically on increasing throughput of coefficient of thermal expansion (CTE) measurements with the use of optical strain measurements, called digital image correlation (DIC). Currently, the coefficient of thermal expansion is found through a time intensive process called dilatometry. There are multiple types of dilatometers. One type, a double push rod mechanical dilatometer, uses and LVDT to measure the expansion of a specimen in one direction. It uses a reference material with known properties to determine the CTE of the specimen in question. Testing about 500 samples using the double push rod mechanical dilatometer would take about 2 years if testing Monday through Friday, because the reference material needs to be at a constant temperature and heating must done slowly to ensure no thermal gradients across the rod. A second type, scissors type dilatometer, pinches a sample using a “scissor-like” appendage that also uses a LVDT to measure thermal expansion as the sample is heated. Finally, laser dilatometry, was created to provide a non-contact means to measure thermal expansion. This process greatly reduces the time required to setup a measurement but is still only able to measure one sample at a time. The time required to test 500 samples gets reduced to 3.5 weeks. Additionally, to measure expansion in different directions, multiple lasers must be used. Dr. Fitzgerald solved this conundrum by using an optical measurement technique called digital image correlation to create strain maps in multiple orientations as well as measuring multiple samples at once. Using this technique, Dr. Fitzgerald can test 500 samples, conservatively, in 2 days.

36 MATERIALS SCIENCE↗

NASA NTRS1978

A critical examination of expansion tunnel performance

An experimental study of the performance of the expansion tunnel for various test gases and range of quiescent acceleration section and nozzle pressure, nozzle geometric area ratio, and nozzle axial station has been performed. Flow diagnostics used to examine expansion tunnel flow characteristics were time histories and profiles of pitot pressure and axial component of flow velocity. The purpose of this study was to determine experimentally what limitations might restrict predicted operational flexibility and the advantages and disadvantages of this mode of operation as compared to the expansion tube. Results are presented which demonstrate the expansion tunnel offers several advantages over the expansion tube, but the severity of the disadvantages of the tunnel makes the expansion tube mode of operation the more desirable for performing hypersonic-hypervelocity aerothermodynamic studies of proposed entry configurations.

Miller, C. G.↗

NASA NTRS1985

A study of plasma expansion phenomena in laboratory generated plasma wakes - Preliminary results

The plasma expansion into the wake of a large rectangular plate immersed in a single-ion, collisionless, streaming plasma has been investigated in the laboratory. Several characteristics of the process involved in 'plasma expansion into vacuum' that have been predicted theoretically were observed, including the creation and motion of a rarefaction wave disturbance; the creation and motion of an expansion front; and the acceleration of ions into the wake at speeds above the ion-acoustic speed. The expansion was limited to early times; i.e., a few ion plasma periods, by the combination of plasma drift speed and vacuum chamber size. This prevented detailed comparison with self-similar theory, but results are in good agreement with numerical simulations and other laboratory experiments for the early time expansion. The conclusion is that the plasma expansion process is the dominant wake filling mechanism in the near wake of a body, whose potential is approximately the plasma space potential.

Wright, K. H., Jr.↗

NASA NTRS1987

Thermal expansion of selected graphite-reinforced polyimide-, epoxy-, and glass-matrix composites

The thermal expansion of continuous carbon-fiber reinforced composites with epoxy-, polyimide-, and borosilicate glass-matrices has been measured and compared. The expansion of a rubber-toughened epoxy-matrix/P75S carbon-fiber composite was very different from the expansion of two different single-phase epoxy-matrix/P75S composites, although all three had the same stacking sequence. Reasonable agreement was obtained between measured thermal expansion data and results from classical laminate theory. Microdamage in the graphite/polyimide laminate, induced by 250 cycles between -156 and 121 C, caused a 53 percent decrease in the coefficient of thermal expansion. The thermal expansion of the graphite/glass laminate was not changed after 100 thermal cycles from -129 to 38 C; however, a residual strain of about 10 x 10 to the -6 was observed for the laminate tested.

Tompkins, S. S.↗

NASA NTRS1988

Expansion tube test time predictions

The interaction of an interface between two gases and strong expansion is investigated and the effect on flow in an expansion tube is examined. Two mechanisms for the unsteady Pitot-pressure fluctuations found in the test section of an expansion tube are proposed. The first mechanism depends on the Rayleigh-Taylor instability of the driver-test gas interface in the presence of a strong expansion. The second mechanism depends on the reflection of the strong expansion from the interface. Predictions compare favorably with experimental results. The theory is expected to be independent of the absolute values of the initial expansion tube filling pressures.

Gourlay, Christopher M.↗

NASA NTRS1988

The driver in flares and coronal mass ejections: Magnetic expansion

Chromospheric filaments, and hence the sheared magnetic fields that they trace, are observed to erupt in flares and coronal mass ejections. In the eruption, the filament-traced field is seen to expand in volume. For frozen-in magnetic field and isotropic expansion, the magnetic energy in a flux tube decreases as the flux tube expands. The amount of expansion of the magnetic field and the corresponding decrease in magnetic energy in a filament-eruption flare and/or coronal mass ejection can be estimated to order of magnitude from the observed expansion of the erupting filament. This evaluation for filament-eruption events in which the filament expansion is clearly displayed gives decreases in magnetic energy of the order of the total energy of the accompanying flare and/or coronal mass ejection. This simple expanding flux tube model can also fit the observed acceleration of coronal mass ejections, if it is assumed that the increase in mechanical energy of the mass ejection comes from the magnetic energy decrease in the expansion. These results encourage the view that magnetic expansion such as seen in filament eruptions drives both the plasma particle energization in flares and the bulk mass motion in coronal mass ejections.

Moore, Ronald L.↗

NASA NTRS1989

Rocket nozzle expansion ratio analysis for dual-fuel earth-to-orbit vehicles

Results are reported from a recent study of the effects of Space Shuttle Main Engine expansion ratio modifications, in the cases of both single-stage and two-stage systems. Two-position nozzles were employed; after varying the lower expansion ratio while the higher was held constant at 120, the lower expansion ratio was held constant at 40 or 60 while the higher expansion ratio was varied. The expansion ratios for minimum vehicle dry mass are different for single-stage and two-stage systems. For two-stage systems, a single expansion ratio of 77.5 provides a lower dry mass than any two-position nozzle.

Martin, James A.↗

NASA NTRS1989

Expansion and orthogonalization of measured modes for structure identification

The purpose was to investigate a new simultaneous expansion/orthogonalization method in comparison with two previously published expansion methods and a widely used orthogonalization technique. Each expansion method uses data from an analytical model of the structure to complete the estimate of the mode shape vectors. Berman and Nagy used Guyan expansion in their work with improving analytical models. In this method, modes are expanded one at a time, producing a set not orthogonal with respect to the mass matrix. Baruch and Bar Itzhack's optimal orthogonalization procedure was used to subsequently adjust the expanded modes. A second expansion technique was presented by O'Callahan, Avitabile, and Reimer and separately by Kammer. Again, modes are expanded individually and orthogonalized after expansion with the same optimal technique as above. Finally, a simultaneous expansion/orthogonalization method was developed from the orthogonal Procrustes problem of computational mathematics. In this method modes are optimally expanded as a set and orthogonal with respect to the mass matrix as a result. Two demonstation problems were selected for the comparison of the methods described. The first problem is an 8 degree of freedom spring-mass problem first presented by Kabe. Several conditions were examined for expansion method including the presence of errors in the measured data and in the analysis models. As a second demonstration problem, data from tests of laboratory scale model truss structures was expanded for system identification. Tests with a complete structure produced a correlated analysis model and the stiffness and mass matrices. Tests of various damaged configurations produced measured data for 6 modes at 14 dof locations.

Smith, Suzanne Weaver↗

NASA NTRS1993

Expansion-based passive ranging

A new technique of passive ranging which is based on utilizing the image-plane expansion experienced by every object as its distance from the sensor decreases is described. This technique belongs in the feature/object-based family. The motion and shape of a small window, assumed to be fully contained inside the boundaries of some object, is approximated by an affine transformation. The parameters of the transformation matrix are derived by initially comparing successive images, and progressively increasing the image time separation so as to achieve much larger triangulation baseline than currently possible. Depth is directly derived from the expansion part of the transformation. To a first approximation, image-plane expansion is independent of image-plane location with respect to the focus of expansion (FOE) and of platform maneuvers. Thus, an expansion-based method has the potential of providing a reliable range in the difficult image area around the FOE. In areas far from the FOE the shift parameters of the affine transformation can provide more accurate depth information than the expansion alone, and can thus be used similarly to the way they were used in conjunction with the Inertial Navigation Unit (INU) and Kalman filtering. However, the performance of a shift-based algorithm, when the shifts are derived from the affine transformation, would be much improved compared to current algorithms because the shifts - as well as the other parameters - can be obtained between widely separated images. Thus, the main advantage of this new approach is that, allowing the tracked window to expand and rotate, in addition to moving laterally, enables one to correlate images over a very long time span which, in turn, translates into a large spatial baseline - resulting in a proportionately higher depth accuracy.

Barniv, Yair↗

NASA NTRS1993

Expansion-based passive ranging

This paper describes a new technique of passive ranging which is based on utilizing the image-plane expansion experienced by every object as its distance from the sensor decreases. This technique belongs in the feature/object-based family. The motion and shape of a small window, assumed to be fully contained inside the boundaries of some object, is approximated by an affine transformation. The parameters of the transformation matrix are derived by initially comparing successive images, and progressively increasing the image time separation so as to achieve much larger triangulation baseline than currently possible. Depth is directly derived from the expansion part of the transformation. To a first approximation, image-plane expansion is independent of image-plane location with respect to the focus of expansion (FOE) and of platform maneuvers. Thus, an expansion-based method has the potential of providing a reliable range in the difficult image area around the FOE. In areas far from the FOE the shift parameters of the affine transformation can provide more accurate depth information than the expansion alone, and can thus be used similarly to the way they have been used in conjunction with the Inertial Navigation Unit (INU) and Kalman filtering. However, the performance of a shift-based algorithm, when the shifts are derived from the affine transformation, would be much improved compared to current algorithms because the shifts--as well as the other parameters--can be obtained between widely separated images. Thus, the main advantage of this new approach is that, allowing the tracked window to expand and rotate, in addition to moving laterally, enables one to correlate images over a very long time span which, in turn, translates into a large spatial baseline resulting in a proportionately higher depth accuracy.

Barniv, Yair↗

NASA NTRS1994

Particle and field signatures during pseudobreakup and major expansion onset

The temporal and spatial scales of the onset of two types of substorm events are investigated. These substorms were cases where the expansion onset had precursor localized auroral activation without significant negative bay enhancement, that is, 'pseudobreakup'. High-resolution energetic particle and magnetic field data at synchronous orbit are used for the analysis together with auroral and magnetic field data simultaneously taken from ground-based instrumentation. The auroral structure following the pseudobreakup significantly resembled the major expansion aurora, except in its spatial scale. Typical magnetospheric onset signatures such as tail current diversion, dipolarization, and injection were observed associated with some of the pseudobreakups. The major expansion, on the other hand, consisted of a number of rather localized injections and expansions, each of which had timescales of 2-8 min, a comparable timescale to that of pseudobreakups. This study shows that there does not appear to be any phenomenological differences between pseudobreakups and major expansion onsets. The major difference between pseudobreakups and major expansion onsets would be the number of occurrences, as well as the intensity and the scale size of the magnetospheric source.

Nakamura, Rumi↗