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At least 1,441 records · Page 80

Transition from Vogel-Fulcher-Tammann to Arrhenius Ion-Conducting Behavior in Poly(Ethyl Acrylate)-Based Solid Polymer Electrolytes via Succinonitrile Plasticizer Addition

Solid polymer electrolytes (SPEs) offer potential advantages over liquid electrolytes, including flexibility, safety, and processability. However, they suffer from low room-temperature ionic conductivity. Recently, it has been reported a poly(ethyl acrylate) based (polyEA) SPE, by incorporating 50 wt% of succinonitrile (SN) solid plasticizer, 30 wt% of lithium salt and 5 wt% of fluoroethylene carbonate additive, which achieves a high room-temperature ionic conductivity of 1.01 × 10 −3 S cm −1 (Nat. Nanotechnol, 2022, 17, 768-776). This novel SPE exhibits stability against Li 0 and anodic stability up to 4.9 V vs Li + /Li. However, the specific mechanism responsible for its high ionic conductivity remains elusive. In this work, by adjusting the weight ratio of SN in the SPE, a transition from Vogel-Fulcher-Tammann to Arrhenius ion-conducting behavior is observed. It is demonstrated that the addition of SN leads to the gradual decoupling of Li-ion from the polymer backbone and its coordination with SN, as revealed by 6 Li solid-state nuclear magnetic resonance spectroscopy. As a result, Li-ion migration primarily occurs through SN rather than the segmental motion of the polymer backbone. Performances of the SPE in Cu||Li, Li||Li and a LiFePO 4 ||Li pouch cells are shown to demonstrate the commercial viability of this SPE in Li 0 -anode solid-state batteries.

Electrochemistry↗

Recovery and Time-response Characteristics of Six Thermocouple Probes in Subsonic and Supersonic Flow

Experimental data obtained from three shielded and three unshielded thermocouple probes are presented. Data taken in air at room temperature over the ranges 0.2 to 2.2 Mach number and 0.2 to 2.2 atmospheres total pressure show reproducible systematic variations of recovery with Mach number, ambient pressure, flow angle, and probe design. Time-constant data determined at Mach 0.2 and room temperature and pressure indicate that unshielded probes are several times faster in response to temperature changes than shielded probes.

Stickney, Truman M↗

Preliminary metallographic studies of ball fatigue under rolling-contact conditions

The metallurgical results produced on balls tested in the rolling-contact fatigue spin rig were studied by metallographic examination. Origin and progression of fatigue failures were observed. These evaluations were made on SAE 52100 and AISI M-1 balls fatigue tested at room temperature (80 F) and 200 to 250 F. Most failures originated subsurface in shear; inclusions, structure changes, and directionalism adversely affected ball fatigue life. Structures in the maximum-shear-stress region of the balls of both materials were stable at room temperature and unstable at 200 to 250 F. Failures were of the same type as those found in full-scale bearings.

SURFACES, CONTACT - ROLLING↗

Mechanical Alloying for Making Thermoelectric Compounds

An economical room-temperature mechanical alloying process has been shown to be an effective means of making a homogeneous powder that can be hot-pressed to synthesize a thermoelectric material having reproducible chemical composition. The synthesis of a given material consists of the room temperature thermomechanical-alloying process followed b y a hot-pressing process. Relative to synthesis of nominally the same material by a traditional process that includes hot melting, this s ynthesis is simpler and yields a material having superior thermoelect ric properties.

Huang, Chen-Kuo↗

Effect of Thermal Exposure on the Tensile Properties of Aluminum Alloys for Elevated Temperature Service

Tensile properties were evaluated for four aluminum alloys that are candidates for airframe applications on high speed transport aircraft. These alloys included the Al-Cu-Mg-Ag alloys C415 and C416 and the Al-Cu-Li-Mg-Ag alloys RX818 and ML377. The Al-Cu-Mg alloys CM001, which was used on the Concorde SST, and 1143, which was modified from the alloy used on the TU144 Russian supersonic aircraft, were tested for comparison. The alloys were subjected to thermal exposure at 200 F, 225 F and 275 F for times up to 30,000 hours. Tensile tests were performed on thermally-exposed and as-received material at -65 F, room temperature, 200 F, 225 F and 275 F. All four candidate alloys showed significant tensile property improvements over CM001 and 1143. Room temperature yield strengths of the candidate alloys were at least 20% greater than for CM001 and 1143, for both the as-received and thermally-exposed conditions. The strength levels of alloy RX818 were the highest of all materials investigated, and were 5-10% higher than for ML377, C415 and C416 for the as-received condition and after 5,000 hours thermal exposure. RX818 was removed from this study after 5,000 hours exposure due to poor fracture toughness performance observed in a parallel study. After 30,000 hours exposure at 200 F and 225 F, the alloys C415, C416 and ML377 showed minor decreases in yield strength, tensile strength and elongation when compared to the as-received properties. Reductions in tensile strength from the as-received values were up to 25% for alloys C415, C416 and ML377 after 15,000 hours exposure at 275 F.

Edahl, Robert A., Jr.↗

Synthesis and molecular structure of perhalogenated rhenium-oxo corroles

Abstract As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β -perhalogenation of five ReO meso -tris( para -X-phenyl)corroles, Re[T p XPC](O) (X = CF 3 , H, F, CH 3 , and OCH 3 ), with elemental chlorine and bromine. With Cl 2 , β -octachlorinated products Re[Cl 8 T p XPC](O) were rapidly obtained for X = CF 3 , H, and CH 3 , but X = OCH 3 resulted in overchlorination on the meso -aryl groups. Full β -octabromination proved slower relative to Cu and Ir corroles, but the desired Re[Br 8 T p XPC](O) products were finally obtained for X = H and F after a week at room temperature. For X = CH 3 and OCH 3 , these conditions led to undecabrominated products Re[Br 11 T p XPC](O). Compared to the β -unsubstituted starting materials, the β -octahalogenated products were found to exhibit sharp 1 H NMR signals at room temperature, indicating that the aryl groups are locked in place by the β -halogens, and substantially redshifted Soret and Q bands. Single-crystal X-ray structures of Re[Cl 8 T p CF 3 PC](O), Re[Cl 8 T p CH 3 PC](O), and Re[Br 8 T p FPC](O) revealed mild saddling for one Cl 8 structure and the Br 8 structure. These structural variations, however, appear too insignificant to explain the slowness of the β -octabromination protocols, which seems best attributed to the deactivating influence of the high-valent Re center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vacuum Strength of Two Candidate Glasses for a Space Observatory

The strengths of two candidate glass types for use in a space observatory were measured. Samples of ultra-low expansion glass (ULE) and borosilicate (Pyrex) were tested in air and in vacuum at room temperature (20 C) and in vacuum after being heated to 200 C. Both glasses tested in vacuum showed an increase in strength over those tested in air. However, there was no statistical difference between the strength of samples tested in vacuum at room temperature and those tested in vacuum after heating to 200 C.

Manning, T. a.↗

Fractographic Analysis of HfB2-SiC and ZrB2-SiC Composites

Hafnium diboride-silicon carbide and zirconium diboride-silicon carbide composites are potential materials for high temperature leading edge applications on reusable launch vehicles. In order to establish material constants necessary for evaluation of in-situ fracture, bars fractured in four point flexure were examined using fractographic principles. The fracture toughness was determined from measurements of the critical crack sizes and the strength values, and the crack branching constants were established to use in forensic fractography of materials for future flight applications. The fracture toughnesses range from about 13 MPam (sup 1/2) at room temperature to about 6 MPam (sup 1/2) at 1400 C for ZrB2-SiC composites and from about 11 MPam (sup 1/2) at room temperature to about 4 MPam (sup 1/2) at 1400 C for HfB2-SiC composites.

Mecholsky, J.J., Jr.↗

Compatibility of Steels in Supercritical CO2 at 450°-650°C

Supercritical CO2 (sCO2) power cycles, particularly direct-fired cycles, have the possibility of revolutionizing clean fossil energy. However, in the lower temperature sections of the cycle, lower cost steels are needed in order to lower the cost of the sCO2 technology. Representative 9 and 12%Cr steels and conventional and advanced austenitic steels are being evaluated at 450-650°C using mass change, bulk carbon (C) content and room temperature tensile properties to determine the maximum use temperatures for both direct- and indirect-fired sCO2 cycles. After 1000 h exposures in research grade (RG) sCO2 at 300 bar and RG sCO2 with 1% O2 and 0.1% H2O additions, the results suggest that increasing the Cr content from 9 to 12% yielded no signficant benefit under these conditions but the higher Cr and Ni contents in S31025 provided better compatibility in RG sCO2 at 650°C but limited benefit at 550°C with impurities. For S31609, the formation of Fe-rich oxide after exposure to RG sCO2 at 650°C resulted in both an increase in the bulk C content and a large drop in room temperature ductility. The evidence suggests thin, protective oxides prevented C ingress in these conditions.

Pint, Bruce↗

Irradiation-induced segregation at dislocation loops in CoCrFeMnNi high entropy alloy

To understand the redistribution of alloying elements in high entropy alloys under irradiation, we irradiated a CoCrFeMnNi alloy with 1 MeV Kr ions at room temperature and at 500°C, and characterized with atom probe tomography and transmission electron microscopy. At 500°C, Co and Ni were enriched around the interstitial, faulted and perfect, dislocation loops resulted from the ion irradiation. In contrast, no segregation was observed at room temperature. The inverse Kirkendall effect through vacancy flux, as opposed to the interstitial binding mechanism, was the primary underlying process attributing to the observed segregation. In addition, a ring-shaped segregation pattern was observed at the faulted dislocation loops, indicating a non-equilibrium nature of the defect clustering and solute segregation process in CoCrFeMnNi under irradiation at high temperature.

36 MATERIALS SCIENCE↗

Effect of blackbody radiation on the threshold for two-electron photodetachment of H/-/

The threshold law of the titled process, which is of the same form as that for electron-impact ionization of H, can experimentally be contaminated by simultaneous single photodetachment and Rydberg excitation of the residual atom, followed by ionization of the Rydberg atom by (room-temperature) blackbody photons. This gives a signal indistinguishable from direct double photodetachment. The correction is here calculated and shown to be finite at the double photodetachment threshold, and to have, possibly, an implication about the form of the threshold law itself. However, at room temperature its contribution is found to be small as it pertains to a recently initiated experiment at the Los Alamos Meson Physics Facility for available energies greater than a millivolt above threshold. The temperature dependence of the correction is shown to be large (k/B/T) to the 7/2; thus at higher temperatures the effect may be observable.

Temkin, A.↗

Effects of Fiber Coatings on Tensile Properties of Hi-Nicalon SiC/RBSN Tow Composites

Uncoated Hi-Nicalon silicon carbide (SiC) fiber tows and those coated with a single surface layer of pyrolytic boron nitride (PBN), double layers of PBN/Si-rich PBN, and boron nitride (BN)/SiC coatings deposited by chemical vapor deposition (CVD) method were infiltrated with silicon slurry and then exposed to N2, for 4 hr at 1200 and 1400 C. Room temperature ultimate tensile fracture loads and microstructural characterization of uncoated and CVD coated Hi-Nicalon SiC fiber reinforced reaction-bonded silicon nitride (RBSN) tow composites were measured to select suitable interface coating(s) stable under RBSN processing conditions. Results indicate that room temperature ultimate fracture loads of the uncoated Hi-Nicalon SiC/RBSN tow composites nitrided at both temperatures were significantly lower than those of the uncoated Hi-Nicalon tows without slurry infiltration. In contrast, all CVD coated Hi-Nicalon SiC/RBSN tow composites retained a greater fraction of the dry tow fracture load after nitridation at 1200 C, but degraded significantly after nitridation at 1400 C. Reaction between metal impurities (Fe and Ni) present in the attrition milled silicon powder and uncoated regions of SiC fibers appears to be the probable cause for fiber degradation.

Bhatt, Ramakrishna T.↗

Determination of (alpha)-dialkylamino acids and their Enantiomers in Geological Samples by High-Performance Liquid Chromatography after Dervatization with a Chiral Adduct of (omicron)-Phthaldialdehyde

Derivatization with (omicron)-phthaldialdehyde (OPA) and the chiral thiol N-acetyl-L-cysteine (NAC) is a convenient and sensitive technique for the HPLC detection and resolution of protein amino acid enantiomers. The kinetics of the reaction of OPA-NAC with (alpha)-dialkylamino acids was investigated. The fluorescence yield of (alpha)-dialkylamino acids was only about 10% of that of protein amino acids when the derivatization was carried out at room temperature for 1-2 min, which is the procedure generally used for protein amino acid analyses. The fluorescence yield of (alpha)-dialkylamino acids can be enhanced by up to ten-fold when the derivatization reaction time is increased to 15 min at room temperature. The OPA-NAC technique was optimized for the detection and enantiomeric resolution of a-dialkylamino acids in geological samples which contain a large excess of protein amino acids. The estimated detection limit for a-dialkylamino acids is 1-2 pmol, comparable to that for protein amino acids.

Zhoa, Meixun↗

Hot Hydrogen Exposure Degradation of the Strength of Mullite

This study deals with the corrosion of near stoichiometric mullite (3Al2O3-2SiO2) by pure dry hydrogen gas. Exposure of the mullite samples was at temperatures of 1050 and 1250 C for times up to 500 hours. Preferential attack of the alumino-silicate glass present in the grain boundaries of the mullite occurred after 125 hours at 1250 C. Hydrogen scrubbing of the SiO2 from the glassy grain boundaries and the mullite grains yielded a porous alumina-rich surface. The room temperature strength increased after short exposure times at 1250 C (up to 125 hours), then decreased by 53 percent after exposure for 500 hours. At 1050 C, all exposure times (25 to 500 hours) decreased the strength. After 500 hours in hydrogen at 1050 C, the room temperature strength of mullite decreased 22 percent. We also observed a rapid 25 percent strength loss after short exposure times at 1050 C. This is attributed to the calcium/hydrogen assisted crystallization of the glassy, grain-boundary phase.

Herbell, Thomas P.↗

The Impact of Structural Distortions on the Magnetism of Double Perovskites Containing 5d 1 Transition-Metal Ions

Five double perovskites, each containing a transition-metal ion with a 5d 1 configuration, have been studied to better understand the surprising diversity of magnetic ground states seen in these isoelectronic compounds. Ba 2 ZnReO 6 adopts the cubic double perovskite structure and magnetically orders below 16 K, with a canted ferromagnetic structure and a saturated magnetization of ~0.24 μ B /Re. X-ray magnetic circular dichroism indicates a substantial orbital moment of approximately 0.4 μ B /Re that opposes the spin moment. The structures of Ba 2 NaOsO 6 (canted ferromagnet, T C = 7 K) and Ba 2 LiOsO 6 (antiferromagnet, T N = 8 K) are reinvestigated using time-of-flight neutron powder diffraction and found to crystallize with the cubic double perovskite structure. No evidence for a structural distortion can be found in either compound down to 10 K. Ba 2 CdReO 6 is also cubic at room temperature but undergoes a structural transition upon cooling below ~180 K to a tetragonal structure with I4/m symmetry that involves compression of the Re–O bonds that are parallel to the c-axis. Sr 2 LiOsO 6 shows a similar tetragonal distortion at room temperature and maintains that structure down to 10 K. Surprisingly, the Os-centered octahedron in Sr 2 LiOsO 6 is distorted in the opposite direction, exhibiting an elongation of the Os–O bonds along the c-axis. Differences in the distortions of the octahedra lead to different magnetic ground states, antiferromagnetic (T N = 4 K) for Ba 2 CdReO 6 and spin glass (T g = 30 K) for Sr 2 LiOsO 6 . Theoretical modeling shows that the varied magnetic behaviors of double perovskites containing 5d 1 ions are closely tied to crystallographic distortions. Furthermore, these distortions remove the degeneracy of the 5d t 2g orbitals, leading to changes in orbital occupation that ultimately determine which of the several competing magnetic ground states is favored.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving the low temperature ductility of NiAl

The intermetallic NiAl exhibits excellent potential as a structural material for application in air-breathing and single-stage-to-orbit engines. Unfortunately NiAl is brittle at ambient temperature, which is partly attributed to the lack of five independent slip systems as required by von Mises criterion for uniform, volume conserving deformation since the operative group of zone axes (100) slip offers only three independent slip systems. Isostructural FeAl, however, deforms by group of zone axes (111) slip at room temperature which provides five independent slip systems. Thus, it was decided to macroalloy NiAl with Fe to promote group of zone axes (111) slip thereby possibly improving the ductility. For Ni - 30 at. (percent) Al - 20 at. (percent) Fe having essentially bcc microstructure indicated up to 6 percent tensile elongation combined with high yield strength (about 800 MPa). The results compare favorably with those of stoichiometric Ni - 50 at. (percent) Al which, however, deforms by group of zone axes (100) slip at room temperature. The multi-phase alloy approach has proven even more successful for Ni - 20 at. (percent) Al - 30 at. (percent) Fe. The high temperature ductility of the multi-phase alloy was attributed to deformation transfer across interphase boundaries and the crack stopping action of the constituent gamma/gamma' phase. While the constituent phase became increasingly brittle, the beta' phase became more ductile at elevated temperatures. Thus the multi-phase alloy did not exhibit any elevated temperature embrittlement. Similarly, while the beta' phase became weak at high temperatures, the gamma/gamma' phase exhibited better strength retention leading to the improved elevated temperature strength of the multi-phase alloy. Thus, the multi-phase alloy benefits from both its constituent phases, with each phase alleviating the disadvantages associated with the other phase over any temperature range. The multi-phase alloy approach is suggested as a possible approach to designing intermetallic-based alloys.

Guha, Sumit↗

Change of Exposure Time Mid-test in High Temperature DIC Measurement

Performing digital image correlation (DIC) at extreme temperatures has been greatly challenging due to the radiation which saturates the camera sensor. At such high temperatures, the light intensity emitted from an object is occasionally so powerful that the acquired images are overwhelmingly saturated. This induces data loss, potentially ruining the test, thus requiring the user to restart the test. For this reason, selection of an appropriate camera sensitivity plays a crucial role prior to beginning the test. Exposure time is a factor contributing to camera sensitivity and it is the easiest setting to manipulate during the test since it introduces minimal errors when comparing to other factors, especially in quasi-static tests. This paper examines the influence of changing exposure time mid-test on DIC measurement uncertainty. The investigation was conducted by rigid body motion experiments at room temperature and 1600 ◦C, respectively. Thereby, some recommendations are given to help DIC users assess their images at room temperature to extrapolate the exposure at extreme temperatures along with accompanying solutions to salvage data at high temperature.

Digital Image Correlation↗

Effects of electron irradiation and temperature on 1 ohm-cm and 10 ohm-cm silicon solar cells

One OHM-cm and 10 OHM-cm silicon solar cells were exposed to 1.0 MeV electrons at a fixed flux of 10 to the 11th power e/sq cm/sec and fluences of 10 to the 13th power, 10 to the 14th power and 10 to the 15th power e/sq.cm. 1-V curves of the cells were made at room temperature, - 63 C and + or - 143 C after each irradiation. A value of 139.5 mw/sq cm was used as AMO incident energy rate per unit area. The 10 OHM-cm cells appear more efficient than 1 OHM-cm cells after exposure to a fluence greater than 10 to the 14th power e/sq cm. The 1.0 MeV electron damage coefficients for both 1 OHM-cm and 10 OHM-cm cells are somewhat less than those for previously irradiated cells at room temperature. The values of the damage coefficients increase as the cell temperatures decrease. Efficiencies pertaining to maximum power output are about the same as those of n on p silicon cells evaluated previously.

Nicoletta, C. A.↗