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At least 19 records

Stress relaxation of low pressure plasma-sprayed NiCrAlY alloys

The stress relaxation behavior of three NiCrAlY alloys that are commonly used as bond coats for thermal barrier coatings (TBCs) has been directly measured. The relaxation study was conducted at temperatures of 800-1000 C and over a wide range of stresses. It was established that all three bond coat alloys relaxed quite rapidly at temperatures of 900 C and above. Since the upper use temperatures for bond coats in gas turbine engines are between 900 and 1000 C, bond coat relaxation is expected to occur in service. Therefore, relaxation of the bond coat has the potential to affect TBC life. Furthermore, the relaxation differences observed between the three alloys offers a possible explanation for the differences in TBC life observed for these bond coats. While bond coat relaxation is expected to occur for a TBC in service, the mechanism for a relaxation effect on TBC life, if it exists, is yet to be determined.

Brindley, W. J.↗

Stress relaxation of low pressure plasma-sprayed NiCrAlY alloys

The stress relaxation behavior of three NiCrAlY alloys that are commonly used as bond coats for thermal barrier coatings (TBCs) has been directly measured. The relaxation study was conducted at temperatures of 800-1000 C and over a wide range of stresses. It was established that all three bond coat alloys relaxed quite rapidly at temperatures of 900 C and above. Since the upper use temperatures for bond coats in gas turbine engines are between 900 and 1000 C, bond coat relaxation is expected to occur in service. Therefore, relaxation of the bond coat has the potential to affect TBC life. Furthermore, the relaxation differences observed between the three alloys offers a possible explanation for the differences in TBC life observed for these bond coats. While bond coat relaxation is expected to occur for a TBC in service, the mechanism for a relaxation effect on TBC life, if it exists, is yet to be determined.

Brindley, W. J.↗

Low-temperature relaxations in amorphous polyolefins

The dynamic mechanical relaxation behavior of two series of amorphous polyolefins, was investigated from 4.2 K to the glass transition. Most of the polymers show a damping maximum or plateau in the 40 to 50 K region. Various mechanisms which have been suggested for cryogenic relaxations in amorphous polymers are considered as they might relate to the polyolefins. Two secondary relaxation processes above 80 K are distinguished. A relaxation at about 160 K (beta) in the second and third member of each series is associated with restricted blackbone motion. This process requires a certain degree of chain flexibility since it is not observed in the first member of each series. A lower temperature process (gamma) is observed in each member of the second series and is attributed to motion of the ethyl side group.

Hiltner, A.↗

Preparation and Dielectric Measurements of the Rare Earth Green Phases R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb)

It has been demonstrated that R2BaCuO(5-x) (R = Y, Sm, Gd, Dy, Ho, Er, Yb) does not undergo significant densification unless the sintering temperatures are near the incongruent melting point or the sintering times are long. Good quality powders of Y2BaCuO(5-x) have been synthesized by using oxide raw materials or precursors such as acetates and nitrates. The acetates- and the nitrates-derived yttrium green phase resulted in finer particle sizes, acceptable dielectric properties and lower melting temperatures than those processed via oxide raw materials. The hot pressing technique has been employed to produce a dense R2BaCuO(5-x) (R=Y,Gd) substrate with satisfactory dielectric properties. Reactivity to reducing conditions, i.e. graphite die, limited the optimization of the properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO,.,,. Oxygen treatment at 950 OC has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. A high sensitivity to the annealing atmosphere has been demonstrated in Y2BaCuO(5-x). Oxygen treatment at 950 C has been shown to improve the dielectric properties while treatment in nitrogen, at the same temperature, degraded desirable properties. The dielectric constants of the rare earth green phases R2BaCuO(5-x) were found to be low. Relaxation peaks were detected at low temperatures (T less than 150 K) and at high temperatures (150 less than T greater than 420 K). The dielectric losses and conductivities at 77 K were measured to be in the range of 10(exp -4) and 10(exp -12) (Omega-cm)(exp -1), respectively. Many parameters were found to exhibit dependencies on the rare earth cation sizes.

Gonzalez-Titman, Carlos↗

MgADP Promotes Myosin Head Movement toward Actin at Low [Ca 2+ ] to Increase Force Production and Ca 2+ -Sensitivity of Contraction in Permeabilized Porcine Myocardial Strips

Myosin cross-bridges dissociate from actin following Mg 2+ -adenosine triphosphate (MgATP) binding. Myosin hydrolyses MgATP into inorganic phosphate (P i ) and Mg 2+ -adenosine diphosphate (ADP), and release of these hydrolysis products drives chemo-mechanical energy transitions within the cross-bridge cycle to power muscle contraction. Some forms of heart disease are associated with metabolic or enzymatic dysregulation of the MgATP-MgADP nucleotide pool, resulting in elevated cytosolic [MgADP] and impaired muscle relaxation. We investigated the mechanical and structural effects of increasing [MgADP] in permeabilized myocardial strips from porcine left ventricle samples. Sarcomere length was set to 2.0 µm at 28 °C, and all solutions contained 3% dextran T-500 to compress myofilament lattice spacing to near-physiological values. Under relaxing low [Ca 2+ ] conditions (pCa 8.0, where pCa = -log 10 [Ca 2+ ]), tension increased as [MgADP] increased from 0-5 mM. Complementary small-angle X-ray diffraction measurements show that the equatorial intensity ratio, I 1,1 /I 1,0 , also increased as [MgADP] increased from 0 to 5 mM, indicating myosin head movement away from the thick-filament backbone towards the thin-filament. Ca 2+ -activated force-pCa measurements show that Ca 2+ -sensitivity of contraction increased with 5 mM MgADP, compared to 0 mM MgADP. These data show that MgADP augments tension at low [Ca 2+ ] and Ca 2+ -sensitivity of contraction, suggesting that MgADP destabilizes the quasi-helically ordered myosin OFF state, thereby shifting the cross-bridge population towards the disordered myosin ON state. Together, these results indicate that MgADP enhances the probability of cross-bridge binding to actin due to enhancement of both thick and thin filament-based activation mechanisms.

60 APPLIED LIFE SCIENCES↗

Multiamorphous Phases in Diketopyrrolopyrrole-Based Conjugated Polymers: From Bulk to Ultrathin Films

The glass transition temperature (T g ) of conjugated polymers is a crucial physical parameter that governs their mechanical and electrical properties for applications from sensor technology to skin-like electronics. Despite some well-developed methods that exist for detecting T g of conjugated polymers, there is still a need for the combination of advanced calorimetric methodologies to characterize T g in a broad range of temperatures and scales from bulk to nanometer-thin films. In this work, alternating current (ac) chip calorimetry and flash differential scanning calorimetry (flash DSC) are applied to successfully identify the Tgs and segmental relaxations of conjugated polymers. The detected relaxations were interpreted, in agreement with existing observations in similar systems, as a side-chain relaxation (low temperature), mobile amorphous fractions (MAF), and rigid amorphous fractions (RAF). T g s of MAF and RAF increase and decrease with increasing size of fused thiophene units in the backbone, respectively. The T g s of diketopyrrolopyrrole-based conjugated polymer thin films are also identified by the same method, with both T g s showing a decreased value compared to those of bulk samples. Furthermore, the weight fractions of MAF and RAF with various film thicknesses are qualitatively analyzed based on the heat capacity step of each amorphous fraction during the glass transition. This facile method gives insights into the physical nature of amorphous phases in conjugated polymers for better revealing their structure-property relationships, which will guide the designs of new materials with optimized electrical and mechanical properties in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low frequency dielectric relaxation in boracites

In order to elucidate the nature of the imperfections which adversely affect pyroelectric processes in boracites, the thermal and dispersive characteristics of the low frequency dielectric response in iron-iodide boracite (Fe3B7O13I) and copper-chloride boracite (Cu3B7O13Cl) have been investigated. These characteristics were measured as a function of crystallographic orientation and applied field in both the ferroelectric and paraelectric states. The low frequency dielectric relaxation of 100 line oriented multi-domain copper-chloride boracite clearly indicates the dipole nature of the lattice imperfections. The activation energies calculated from a noninteracting Debye model, are 0.53 eV in the ferroelectric phase and 0.10 eV in the paraelectric phase.

Kim, Q.↗

Understanding the microstructural evolution of hypersaline cemented paste backfill with low-field NMR relaxation

Highlights: • Microstructural evolution of CPB, prepared with tap and hypersaline water, is monitored using low-field NMR relaxometry. • T{sub 1} and T{sub 2} NMR relaxation measurements compared with mechanical strength via UCS tests • Hypersaline mixing water results in slower structural evolution and lower mechanical strength. Cemented paste backfill (CPB) comprising mineral tailings, binders and mixing water is an important potential support material in the mining industry. As the mechanical properties of CPB are significantly influenced by its microstructural characteristics the development of measurement tools to better understand its pore structure evolution is important for its increased utilisation. This study reports the application of low-field nuclear magnetic resonance (NMR) relaxation time measurements to characterise the microstructural evolution of CPB materials over 56 days of hydration, contrasting common tap water and hypersaline water (~22 wt% salt) as mixing water. Distinct NMR relaxation time populations were evidenced within each CPB sample, revealing the presence of both capillary (T{sub 1,2} ≈ 10 ms) and gel pore water (T{sub 1,2} ≈ 300–500 μs), with time-dependent relaxation measurements facilitating characterisation of capillary pore structure evolution over the hydration period assessed. Hypersaline samples demonstrated a time-lag in this measured capillary pore evolution, relative to those hydrated with tap water, while pore structure evolution rates were observed to increase with increased CPB binder content. Further, both T{sub 1} and T{sub 2} NMR relaxation times were found to correlate with the uniaxial compressive strength of the CPB materials investigated, facilitating the formulation of a predictive correlation function between NMR relaxation characteristics and mechanical properties.

36 MATERIALS SCIENCE↗

Low-temperature rotational relaxation in gaseous H2 and D2

Various potentials have been used for generating scattering cross sections for rotational transitions in hydrogen isotope systems. Low-temperature rates were calculated and the relaxation times compared with the results of sound absorption experiments. It is seen that the existing potentials could still be improved since they do not exactly reproduce the experimental results.

Ramaswamy, R.↗

Design and implementation of a J -coupled spectrometer for multidimensional structure and relaxation detection at low magnetic fields

In recent years, it has been realized that low and ultra-low field (mT-nT magnetic field range) nuclear magnetic resonance (NMR) spectroscopy can be used for molecular structural analysis. However, spectra are often hindered by lengthy acquisition times or require large sample volumes and high concentrations. Here, we report a low field (50 µT) instrument that employs a linear actuator to shuttle samples between a 1 T prepolarization field and a solenoid detector in a laboratory setting. The current experimental setup is benchmarked using water and 13 C-methanol with a single scan detection limit of 2x10 20 spins (3 μL, 55 M H 2 O) and detection of 2.9x10 19 (200 μL, 617 mM 13 C-methanol) spins with signal averaging. The system has a dynamic range of >3 orders of magnitude. Investigations of room-temperature relaxation dynamics of 13Cmethanol show that sample dilution can be used in lieu of sample heating to acquire spectra with linewidths comparable to high-temperature spectra. These results indicate that the T 1 and T 2 mechanisms are governed by both the proton exchange rate and the dissolved oxygen in the sample. Finally, a 2D correlation spectroscopy (COSY) experiment is reported, performed in the strong coupling regime that resolves the multiple resonances associated with the heteronuclear Jcoupling. The spectrum was collected using 10 times less sample and in less than half the time from previous reports in the strong coupling limit.

47 OTHER INSTRUMENTATION↗

Measurements in the near-wall region of a relaxing three-dimensional low speed turbulent air boundary layer

An experimental investigation was conducted at selected locations of the near-wall region of a three dimensional turbulent air boundary layer relaxing in a nominally zero external pressure gradient behind a transverse hump (in the form of a 30 deg swept, 5-foot chord wing-type model) faired into the side wall of a low speed wind tunnel. Wall shear stresses measured with a flush-mounted hot-film gage and a sublayer fence were in very good agreement with experimental data obtained with two Preston probes. With the upstream unit Reynolds number held constant at 325,000/ft. approximately one-fourth of the boundary layer thickness adjacent to the wall was surveyed with a single rotated hot-wire probe mounted on a specially designed minimum interference traverse mechanism. The boundary layer (approximately 3.5 in thick near the first survey station where the length Reynolds number was 5.5 million) had a maximum crossflow velocity ratio of 0.145 and a maximum crossflow angle of 21.875 deg close to the wall.

Hebbar, K. S.↗

Exchange and relaxation effects in low-energy radiationless transitions

The effect on low-energy atomic inner-shell Coster-Kronig and super Coster-Kronig transitions that is produced by relaxation and by exchange between the continuum electron and bound electrons was examined and illustrated by specific calculations for transitions that deexcite the 3p vacancy state of Zn. Taking exchange and relaxation into account is found to reduce, but not to eliminate, the discrepancies between theoretical rates and measurements.

Chen, M. H.↗

Nanoscale dynamics during self-organized ion beam patterning of Si. I. Ar + bombardment

X-ray photon correlation spectroscopy (XPCS) is used to investigate the fluctuation dynamics during self- organized nanopatterning of silicon by Ar + bombardment at 65° polar angle. Rich structure is observed in the development of the correlation dynamics as seen in the evolving correlation time τ(q || ) and fluctuation relaxation exponent n(q || ). Furthermore, on length scales of the ripple structure, local structure becomes ever more long lived as coarsening progresses. In addition, τ (q || ) develops a peak on length scales corresponding to the ripple wavelength. As patterning progresses, correlation times become asymmetric between the positive and negative directions, suggesting the possibility of different dynamics on the slopes facing toward and away from the ion beam. Relaxation exponents show evolution from linear dynamics at early times to compressed exponential relaxation at low wave numbers and stretched exponential relaxation at high wave numbers. Compressed exponential behavior is reminiscent of stress relaxation processes observed in glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Relaxation behavior in low-frequency complex conductivity of sands caused by bacterial growth and biofilm formation by Shewanella oneidensis under a high-salinity condition

Complex electrical conductivity is increasingly used to monitor subsurface processes associated with microbial activities because microbial cells mostly have surface charges and thus electrical double layers. Although highly saline environments are frequently encountered in coastal and marine sediments, there are limited data available on the complex conductivity associated with microbial activities under a high-salinity condition. Therefore, we have developed the spectral responses of complex conductivity of sand associated with bacterial growth and biofilm formation under a highly saline condition of approximately 1% salinity and approximately 2 S/m pore water conductivity with an emphasis on relaxation behavior. A column test is performed, in which the model bacteria Shewanella oneidensis MR-1 are stimulated for cell growth and biofilm formation in a sand pack, whereas the complex conductivity is monitored from 0.01 Hz to 10 kHz. The test results indicate that the real conductivity increases in the early stage due to the microbial metabolites and the increased surface conduction with cell growth but soon begin to decrease because of the reduction of charge passages due to bioclogging. However, the imaginary conductivity significantly increases with time, and clear bell-shaped relaxation behaviors are observed with the peak frequency of 0.1–1 Hz, associated with the double-layer polarization of cells and electrically conductive pili and biofilms. The Cole-Cole relaxation model appears to capture such relaxation behaviors well, and the modeling results indicate gradual increases in normalized chargeability and decreases in relaxation time during bacterial growth and biofilm formation in the highly saline condition. Comparison with previous literature confirms that the high-salinity condition further increases the normalized chargeability, whereas it suppresses the phase shift and thus the imaginary conductivity. Our results suggest that the complex conductivity can effectively capture microbial biomass formation in sands under a highly saline condition.

58 GEOSCIENCES↗

On the Efficacy of Repeat Voltage Holds for Conditioning and Calendar Life Testing of Graphite and Silicon Cells

Voltage-hold (V-hold) protocols have shown promise toward calendar lifetime analysis of cells with graphite (Gr) and silicon (Si) anodes. In this work, repeat V-holds are performed on Gr and Si cells paired with lithium iron phosphate cathodes to delineate their beneficial role in formation and conditioning. We find that V-hold at the top of charge supplements constant current cycling in conditioning the cell to higher capacities for both Gr and Si cells after the first V-hold. A reduced order model provides the irreversible capacity proportions of each V-hold. With each repeat V-hold, parasitic loss of lithium to the solid electrolyte interphase (SEI) decreases on both Gr and Si cells. Gr cells show the square-root-of-time capacity loss behavior within 200 h of V-hold, indicative of its fast relaxation and low impact of reference performance test cycles on the SEI growth. Lifetime estimates from repeat V-holds on Gr can reach years. Si exhibits longer transition times from kinetic to diffusion-limited SEI growth, evidenced by the 400 h and 200 h holds showing square-root-of-time and linear behavior, respectively. Lifetime predictions from repeat V-holds on Si only reach 1–2 months, highlighting its limitations. Recommended duration of V-holds for Si cells should be ≥400 h.

25 ENERGY STORAGE↗