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At least 109 records · Page 6

Infrared laser ablation of poly(vinylidene fluoride): The Loss of HF

The mechanism and kinetics of infrared laser ablation of poly(vinylidene fluoride) (PVDF) in vacuum have been investigated to understand how this can be used as a polymer processing technology. The laser heats the surface and initiates decomposition of macromolecules in the molten polymer layer which rapidly leads to production of an ablative flow of polymer decomposition products. There is only a short induction period of up to 2 s before ablation begins. After the initial period, the rate of mass loss increases linearly with the time of laser exposure. Spherical particles with an average diameter of about 100 nm are formed on the surface of the powder coating obtained by laser ablation. Here, the particle distribution ranges from 50 nm to 300 nm. The main gaseous product of ablation is HF from dehydrofluorination. A second important ablation process is the formation of gaseous carbenes generated during secondary reactions. Proposed ablation reactions due to laser-induced thermal dehydrofluorination occur in two stages. In the first stage, a double bond appears in PVDF due to direct loss of HF. Subsequent detachment of HF leads to the appearance of both triple bonds and cumulene bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct measurement of covalent three-center, two-electron M–H–B bonding in Zr and Hf borohydrides using B K-edge XAS

Metal borohydride complexes have long been the subject of intense fundamental interest because of their unconventional metal–ligand bonding that occurs via three-center, two-electron M–H–B bonds. This type of bonding implies significant delocalization of electron density over all three atoms, but the degree of orbital mixing between the metal and boron has been difficult to assess by direct experimental means. Herein, we demonstrate how ligand K-edge X-ray absorption spectroscopy (XAS) conducted at the B K-edge yields evidence of significant covalent M–H–B bonding with Zr and Hf. To accommodate the B K-edge XAS studies, which were conducted under ultra-high vacuum (<10 −8 torr), we prepared a series of new [Zr(RBH 3 ) 4 ] and [Hf(RBH 3 ) 4 ] complexes with substituents that attenuate volatility (R = benzyl, phenyl, mesityl, 2,4,6-triisopropylphenyl, and anthryl). 1 H and 11 B NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction (XRD) studies revealed metal and ligand dependent differences in the BH 3 chemical shifts that correlate to changes in M−B distances and select B–H vibrational stretching modes. The B K-edge XAS spectra of the Zr and Hf complexes yielded a pre-edge feature that was assigned as B 1s → M–H–B π* based on comparison to time-dependent density functional theory (TDDFT) calculations. The pre-edge transitions appear due to covalent mixing between boron and the metal, thereby demonstrating how B K-edge XAS can provide direct evidence of covalent three-center, two electron M–H–B bonding in borohydride complexes using boron as a spectroscopic reporter.

Hansen, Hannah M. [University of Iowa, Iowa City, ↗

Compositional and phase dependence of elastic modulus of crystalline and amorphous Hf 1- x Zr x O 2 thin films

The elastic moduli of amorphous and crystalline atomic layer-deposited Hf 1-x Zr x O 2 (HZO, x = 0, 0.31, 0.46, 0.79, 1) films prepared with TaN electrodes on silicon substrates were investigated using picosecond acoustic measurements. The moduli of the amorphous films were observed to increase between 211 ± 6 GPa for pure HfO 2 and 302 ± 9 GPa for pure ZrO 2 . In the crystalline films, it was found that the moduli increased upon increasing the zirconium composition from 248 ± 6 GPa for monoclinic HfO 2 to 267 ± 9 GPa for tetragonal ZrO 2 . Positive deviations from this increase were observed for the Hf 0.69 Zr 0.31 O 2 and Hf 0.54 Zr 0.46 O 2 compositions, which were measured to have moduli of 264 ± 8 GPa and 274 ± 8 GPa, respectively. These two compositions contained the largest fractions of the ferroelectric orthorhombic phase, as assessed from polarization and diffraction data. The biaxial stress states of the crystalline films were characterized through sin 2 (ψ) x-ray diffraction analysis. The in-plane stresses were all found to be tensile and observed to increase with the increasing zirconium composition, between 2.54 ± 0.6 GPa for pure HfO 2 and 5.22 ± 0.5 GPa for pure ZrO 2 . The stresses are consistent with large thermal expansion mismatches between the HZO films and silicon substrates. Furthermore, these results demonstrate a device-scale means to quantify biaxial stress for investigation on its effect on the ferroelectric properties of hafnia-based materials.

36 MATERIALS SCIENCE↗

Electron irradiation effects on the optical properties of Hf- and Zn-doped β -Ga 2 O 3

Optical and electrical properties of Hf- and Zn-doped β-Ga 2 O 3 samples, which are n-type and insulating, respectively, were altered via high-energy electron irradiation at 2.5 or 0.5 MeV. The β-Ga 2 O 3 :Hf samples irradiated with 2.5 MeV electrons experienced a color change from blue to yellow and a large drop in conductivity, attributed to the creation of gallium vacancies, which compensate donors. This irradiation resulted in the absence of free carrier absorption and the presence of Cr 3+ photoluminescence (PL). PL mapping prior to irradiation revealed optically active ZnO precipitates that formed during the growth of β-Ga 2 O 3 :Zn. These precipitates have a 384 nm (3.23 eV) stacking fault emission in the core; in the outer shell of the precipitate, the PL blue-shifts to 377 nm (3.29 eV) and a broad defect band is observed. After 0.5 MeV electron irradiation, the defect band broadened and increased in intensity. The blue PL band (435 nm) of β-Ga 2 O 3 was enhanced for both Hf- and Zn-doped samples irradiated with 0.5 MeV. This enhancement is correlated with an increase in oxygen vacancies.

36 MATERIALS SCIENCE↗

Measurement of the 175 Hf half-life

Hafnium-175 is a useful radioisotope for numerous applications; however, its evaluated half-life (70 ± 2 days) has a large uncertainty. To enable a new measurement of the half-life, 175 Hf was produced via proton irradiation of natural lutetium and chemically purified. The 175 Hf sample was counted approximately once a month with three high-purity germanium detectors for 13 months (~5.5 half-lives). A 133 Ba standard was counted in an identical manner to quantify systematic uncertainties over the measurement period. In conclusion, the measured 175 Hf half-life is 69.90 ± 0.07 days, in agreement with the evaluated value, but with significantly reduced uncertainty.

150 ≤ A ≤ 189↗

Dark Matter Constraints from Isomeric 178⁢m Hf

In this article, we describe a first measurement of the radiation from a 178⁢m Hf sample to search for dark matter. The $\gamma$ flux from this sample, possessed by Los Alamos National Laboratory nuclear chemistry, was measured with a Ge detector at a distance of 1.2 m due to its high activity. We search for $\gamma$’s that cannot arise from the radioactive decay of 178⁢m Hf but might arise from the production of a nuclear state due to the inelastic scattering with dark matter. The limits obtained on this $\gamma$ flux are then translated into constraints on the parameter space of inelastic dark matter. Finally, we describe the potential reach of future studies with 178⁢m Hf.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Examining the Performance of MIL-STD-188-110D Waveform 0 Against FBMC-SS Over Skywave HF Channels

This paper provides a comprehensive performance comparison between a current robust military waveform; namely, MIL-STD-188-110D, Waveform 0, and a filter bank multicarrier spread-spectrum (FBMC-SS) waveform proposed for communications through ionospheric/skywave HF channels. Waveform 0 is effectively a direct sequence spread spectrum waveform that uses Walsh multi-codes to enhance the information transmission rate. It may thus be referred to as Walsh-DSSS. FBMC-SS, on the other hand, makes use of filter banks to provide excellent performance when the received signal is subject to partial band interference. Successful application of FBMC-SS for communications across skywave HF channels has been previously demonstrated, both theoretically and through experimental work. However, very little has been done to contrast FBMC-SS against Walsh-DSSS. The goal of this paper is to first add new features to FBMC-SS to bring it on par with Walsh-DSSS. These features include: (i), introduction of multi-codes that achieve a comparable (or better) data rate to Walsh-DSSS; and (ii), addition of a scrambling step applied to the multi-codes to make the receiver detection robust against widely spread multipaths. With this established, in the second part of the paper, we examine the performance of the developed FBMC-SS against Walsh-DSSS when both are applied for communications across skywave HF channels. The two waveforms are compared both through a theoretical study and through experimental works across several skywave channels ranging from hundreds to thousands of kilometers.

42 ENGINEERING↗

Impact of HF-CRPA CCQE Model on the Latest NOvA Results

NOvA is a long-baseline neutrino experiment based at Fermilab, dedicated to measuring various neutrino oscillation parameters. Recently, the NOvA collaboration presented new results at NEUTRINO 2024. A significant enhancement in the modeling of charged-current quasi elastic (CCQE) interactions has been achieved with the implementation of the Hartree-Fock (HF) mean-field model, incorporating continuum random phase approximation (CRPA) corrections. This HF-CRPA model offers substantial improvements in the low-energy region. In this presentation, I will discuss the impact of the HF-CRPA model on the latest three-flavor oscillation results of the NOvA experiment.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

TEX-Hf Assemblies: Highly Enriched Uranium Plates with Hafnium Using Polyethylene Moderator and Polyethylene Reflector

This report documents the integral experiment evaluation and publication for IER-532 (TEX-Hf), Thermal/Epithermal eXperiments (TEX) with highly enriched uranium (HEU) fuel and hafnium (Hf), moderated and reflected by polyethylene. The design of TEX-Hf is a variation of IER-297 (TEX-HEU), with the inclusion of hafnium as a diluent material. The experiment and evaluation include seven configurations, all of which were acceptable as benchmark cases. These benchmark cases provide validation for hafnium in the thermal, intermediate, and fast neutron energy regimes by maximizing the sensitivity in k eff to the hafnium cross sections. The evaluation was reviewed and accepted by the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Technical Review Group on April 17, 2024, and was submitted to the ICSBEP in August 2024 following subgroup approval.

42 ENGINEERING↗

The uses and limitations of HF standard broadcasts for time and frequency comparison

The most practical methods of using high-frequency (HF) broadcasts for frequency and time comparison are reviewed. Although standard broadcast and receiving equipment has improved vastly throughout the past fifty years, the HF propagation medium is no more stable today than it was a half century ago. Doppler shift resulting from changes in the effective height of the ionosphere typically limits the usable accuracy of received high frequencies to a few parts in 10 to the 7th power. At locations beyond groundwave range of the transmitter, uncertainties in path delay generally restrict the usable accuracy of HF time signals to the order of a millisecond. Signal-averaging techniques are sometimes employed to extract frequency or time signals from a noisy background.

Stanley, J. T.↗

Effects of C and Hf concentration on the mechanical properties of wrought superalloys based on NASA IIB-11 produced from prealloyed powders

This work describes the effects of C and Hf concentration on the mechanical properties of NASA IIB-11, a candidate material for advanced-temperature gas turbine engine disks. IIB-11 and four alloys of varied C and Hf concentrations were produced as cross-rolled disks from hot-isostatically pressed powder billets. The lower C, higher Hf modification exhibited the best mechanical properties at 760 C and below. These properties were at least equivalent to those of other candidate alloys for advanced temperature disks. Because of their finer grain sizes, all of these powder metallurgy alloys had lower rupture strength, however, than that achieved previously in conventionally processed IIB-11.

Miner, R. V., Jr.↗

HF excited instabilities in space plasmas

It has now become technologically feasible to construct ground-based HF radar systems which can deliver RF energy to the ionospheric plasma, with power densities sufficient to alter the ionospheric electron thermal budget and plasma characteristics. Effects produced by a ground-based transmitter of a power aperture of the order of 10,000 Mw sq m in the frequency range from 4 to 12 MHz are shown in a graph. Another graph presents a profile of electron gas temperature enhancement due to energy deposition by a high power HF transmitter. The conduction of high-power HF ionospheric plasma experiments is discussed. Attention is given to plasma instabilities, wave-particle acceleration effects, spacial and time scales, parametric instabilities, spread-F, and the possibility of placing high power-aperture radars on an orbiting space platform.

Carlson, H. C., Jr.↗

Measurements of pressure-induced shifts in the 1-0 and 2-0 bands of HF and in the 2-0 bands of HCl-35 and HCl-37

Fourier absorption spectra of HCl and HF measured at room temperature and low pressures were found to indicate pressure-induced shifts of the spectral lines at gas pressures of only 10 torr. Self-induced shifts were determined for the HF 2-0 band and for the HCl-35 and HCl-37 2-0 bands, and shift oscillations in the 2-0 bands due to near-resonant dipole-dipole interactions between the two gases were also evaluated. Separate measurements of pressure-induced shifts in the HF 1-0 and 2-0 bands and in both isotopic HCl bands were obtained using argon, neon, nitrogen, and CO2 separately as the perturbing gases.

Guelachvili, G.↗

Lu-Hf total-rock isochron for the eucrite meteorites

The isotope Lu-176 (2.6% of natural lutetium) decays by beta(-) to Hf-176, with a long half life. The first Lu-Hf isochron is presented. The eucrite meteorites, a suite of planetary igneous rocks of known age, 4,550 Myr, define a 10-point total-rock isochron with a slope of 0.0934 + or - 40, leading to a value of 3.53 + or - 0.14 x 10 to the 10th yr for the beta(-) decay half life of Lu-176. The isochron intercept of 0.27973 + or - 12 gives the initial Hf-176/Hf-177 for the inner solar system at the time of accretion.

Patchett, P. J.↗

Thermal response of the F region ionosphere in artificial modification experiments by HF radio waves

The thermal response of the nighttime F region ionosphere to local heating by HF radio waves has been observed with the incoherent scatter radar at Arecibo, Puerto Rico. The observations consist of high-resolution space and time variation of the electron temperature as a high-power HF transmitter is switched on and off with a period 240 s. As soon as the HF transmitter is turned on, the electron temperature begins to rise rapidly in a narrow altitude region near 300 km, below the F2 layer peak. The electron temperature perturbation subsequently spreads over a broader altitude region. The observations are compared with the anticipated thermal response of the ionosphere based on numerical solutions of the coupled time-dependent heat conduction equations for the electron and composite ion gases and are found to be in good agreement over the entire altitude region covered by the observations.

Mantas, G. P.↗

HF produced ionospheric electron density irregularities diagnosed by UHF radio star scintillations

Three observations of radio star intensity fluctuations at UHF are reported for HF ionospheric modification experiments carried out at the Arecibo Observatory. Two observations at 430 MHz and one at 1400 MHz suggest that the the thin phase screen theory is a good approximation to the observed power spectra. It is noted, however, that the theory has to be extended to include antenna filtering. This type of filtering is important for UHF radio star scintillations since the antenna usually has a narrow beamwidth. HF power densities of less than 37 microwatts/sq m incident on the ionosphere give rise to electron density irregularities larger than 13% of the ambient density (at 260 km) having scale sizes of approximately 510 m perpendicular to the geomagnetic field. The irregularities are found to form within 20-25 s after the HF power is turned on. The drift velocities of the irregularities can be estimated from the observed power spectra.

Frey, A.↗

The effect of tantalum on the structure/properties of two polycrystalline nickel-base superalloys: B-1900 + Hf MAR-M247

The microstructure, phase compositions, and phase fractions were studied in conventionally cast B-1900 + Hf and both conventionally cast and directionally solidified MAR-M247 as a function of tantalum concentration. The hot tensile and creep rupture properties of the solutionized and aged MAR-M247-type alloys were also determined as a function of tantalum level. The effects of tantalum on the microstructure and phase compositions of B-1900 + Hf and MAR-M247 (conventionally cast and directionally solidified) were found to be very similar. The addition of tantalum to the as cast and heat treated alloys was shown to cause the partial replacement of the Hf in the MC carbides by Ta, although the degree of replacement was decreased by the solutionizing and aging heat treatment. The gamma prime and minor phase fractions (primarily MC type carbides) both increased approximately linearly with tantalum concentration. The gamma prime phase compositions were relatively insensitive to tantalum variations with the exception of the tantalum and/or hafnium levels. Bulk tantalum additions increased the tantalum, chromium, and cobalt levels of the gamma phase in both alloy series. The increase in the concentrations of the latter two elements in the gamma phase was a result of the decrease in the gamma phase fraction with increasing bulk tantalum concentration and constant gamma/gamma prime partitioning ratio. Tantalum additions increased the yield stress and ultimate tensile strength of the directionally solidified MAR-M247 type alloys and had no significant effect on ductility.

Janowski, G. M.↗

Zircon Lu-Hf systematics: Evidence for the episodic development of Archaean greenstone belts

A combined U-Th-Pb and Lu-Hf isotopic study of zircons was undertaken in order to determine the provenance and age of an Archean granite-greenstone terrain and to test the detailed application of the Lu-Hf system in various Archean zircons. The eastern Wawa subprovince of the Superior province consists of the low grade Michipicoten and Gamitagama greenstone belts and the granitic terrain. The Hf isotopic data indicate that the typical lithological features of a greenstone belt cycle could be accommodated in a crustal growth model that involved decreasing depth of melting in three isotopically distinct reservoirs: mantle, lower crust and upper crust. The model age of the sources given by the intersection of the lower crustal curve with the bulk earth evolution curve is about 2900 My, in good agreement with the zircon U-Pb basement age. This linear array also has a similar intersection age to that of Proterozoic carbonatite complexes. The general convergence of the other reservoir vectors around this age suggests that mantle depletion, crustal extraction and intracrustal differentiation were all part of the same episodic event. It is also apparent that recycling of older basement was important in the formation of many of the later greenstone belt rocks.

Smith, P. E.↗