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At least 19 records

Modulating the thermal conductivity in hexagonal boron nitride via controlled boron isotope concentration

Hexagonal boron nitride (h-BN) has been predicted to exhibit an in-plane thermal conductivity as high as ~ 550 W m –1 K –1 at room temperature, making it a promising thermal management material. However, current experimental results (220–420 m –1 K –1 ) have been well below the prediction. Here, we report on the modulation of h-BN thermal conductivity by controlling the B isotope concentration. For monoisotopic 10 B h-BN, an in-plane thermal conductivity as high as 585 W m –1 K –1 is measured at room temperature, ~ 80% higher than that of h-BN with a disordered isotope concentration (52%:48% mixture of 10 B and 11 B). The temperature-dependent thermal conductivities of monoisotopic h-BN agree well with first principles calculations including only intrinsic phonon-phonon scattering. Our results illustrate the potential to achieve high thermal conductivity in h-BN and control its thermal conductivity, opening avenues for the wide application of h-BN as a next-generation thin-film material for thermal management, metamaterials and metadevices.

36 MATERIALS SCIENCE↗

Seawater pH reconstruction using boron isotopes in multiple planktonic foraminifera species with different depth habitats and their potential to constrain pH and <i>p</i>CO<sub>2</sub> gradients

Boron isotope systematics of planktonic foraminifera from core-top sediments and culture experiments have been studied to investigate the sensitivity ofδ11B of calcite tests to seawater pH. However, our knowledge of the relationship between δ11B and pH remains incomplete for many taxa. Thus, to expand the potential scope of application of this proxy, we report δ11B data for seven different species of planktonic foraminifera from sediment core tops. We utilize a method for the measurement of small samples of foraminifera and calculate the δ11B-calcite sensitivity to pH for Globigerinoides ruber, Trilobus sacculifer (sacc or without sacc), Orbulina universa, Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, Globorotalia menardii, and Globorotalia tumida, including for unstudied core tops and species. These taxa have diverse ecological preferences and are from sites that span a range of oceanographic regimes, including some that are in regions of air–sea equilibrium and others that are out of equilibrium with the atmosphere. The sensitivity of δ11Bcarbonate to δ11Bborate (e.g., Δδ11Bcarbonate/Δδ11Bborate) in core tops is consistent with previous studies for T. sacculifer and G. ruber and close to unity for N. dutertrei, O. universa, and combined deep-dwelling species. Deep-dwelling species closely follow the core-top calibration fo rO. universa, which is attributed to respiration-driven microenvironments likely caused by light limitation and/or symbiont–host interactions. Our data support the premise that utilizing boron isotope measurements of multiple species within a sediment core can be utilized to constrain vertical profiles of pH andpCO2 at sites spanning different oceanic regimes, thereby constraining changes in vertical pH gradients and yielding insights into the past behavior of the oceanic carbon pumps.

54 ENVIRONMENTAL SCIENCES↗

Boron isotopic analysis in bulk silicate materials using the Neoma MS/MS MC-ICP-MS

Boron (B) isotopes are a valuable tracer with applications ranging from geological, environmental, and nuclear studies because B isotopic fractionation is highly sensitive to chemical processes yielding distinct isotopic trends in natural and anthropogenic systems. Despite this wide applicability, there remain relatively few measurements on well-described reference materials and in some cases, poor agreement between various methods. We report a method for boron isotope ratio measurement in solution on the Neoma MS/MS MC-ICP-MS specifically targeting bulk silicates. We evaluate the performance of the method and instrument as it relates to the measurement of the absolute boron isotope ratio ( 10 B/ 11 B). The results indicate that the method produces data in agreement with literature values and that the sample–standard bracketing technique is appropriate for the Neoma MS/MS MC-ICP-MS which has been in use for decades on previous generation instruments. Careful tuning of the MS/MS lenses is required to obtain precision comparable to non MS/MS equipped MC-ICP-MS. With careful tuning, internal and external precisions of ∼0.3‰ were achieved. However, when the MS/MS is not properly tuned external precisions exceed 3‰. Nevertheless, our results for IAEA B-6, BCR-2, BHVO-2 and W-2a reference materials overlap the 1σ range of previously reported 10 B/ 11 B. Data are reported for total boron quantities down to a few tens of nanograms. Our procedure yielded blanks as low as 3 ng but up to 29 ng, making blank corrections important for small samples sizes in the few 10s of nanogram range. We report B isotope ratios for AGV-2G, SL-1G, GSC-2G, GSD-2G, GSE-2G, RLS-132, RLS-140, NKT-1G, and T1-G glass reference materials that have not been previously reported in the literature.

Scott, Sean R. [Pacific Northwest National Laborat↗

Boron isotopes in blue diamond record seawater-derived fluids in the lower mantle

Boron is a quintessential crustal element but its conspicuous presence in diamond – a mantle mineral – raises questions about potential subduction pathways for boron and other volatiles. It has been a long-standing goal to characterize the isotopic composition of boron in blue, boron-bearing (Type IIb) diamonds to reveal its origin. Mineral inclusions indicate that Type IIb diamonds crystallize at transition zone to lower mantle depths, meaning that if the boron is subducted it would trace a pathway of volatile elements into the deep mantle. Here, using off-line laser ablation sampling, we present the first boron isotope compositions, along with trace element contents and carbon isotope compositions, of a suite of blue diamonds mainly sourced from the Cullinan diamond mine in South Africa. The ten analyzed blue diamonds have a wide range in δ 11 B, between -9.2 ± 2‰ and -0.5 ± 2‰, compared to the more restricted range for mid-ocean ridge basalts (-7.1 ± 0.9‰). Carbon isotope values for the blue diamonds range between -20.6 and -1.8‰, with a mode at -17‰, significantly more negative than the main mantle mode at -5‰. Combined, the boron and carbon isotope compositions require fluid input from subducted oceanic lithosphere down into deep mantle source regions of blue diamonds. This finding highlights a deep subduction pathway for volatiles to stoke the source regions of deeply-derived magmas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Separating Stable Boron Isotopes in Uniflow Gas Centrifuges

A variant of a model of a uniflow gas centrifuge for separating a binary mixture of boron isotopes in the trifluoride form, taking account of the interaction of the rotating gas with a stationary cylindrical central body, is proposed. Expressions are obtained for the maximum admissible enrichment and separation factors and the optimal separative power as functions of the radius of the central body. It is shown that a cascade of uniflow gas centrifuges with more than 95% enrichment of boron trifluoride in terms of the {sup 10}B isotope in the requisite quantities for industry can be built in practice.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Influence of boron isotope ratio on the thermal conductivity of uranium diboride (UB 2 ) and zirconium diboride (ZrB 2 )

Uranium diboride is being proposed as an accident tolerant fuel (either as a part of a composite or an 11 B enriched monolithic fuel pellet), while zirconium diboride is often selected as a burnable absorber in conjunction with uranium dioxide fuel pellets. It is therefore important to understand the thermal properties of these materials and examine methods in which they may be improved. The thermal conductivity of UB 2 and ZrB 2 is calculated through atomic scale modelling methods. Lastly, it was found that the boron-isotope ratio has a significant impact on the thermal conductivity of ZrB 2 , but is negligible for UB 2 due to the large electron-phonon scattering.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Lithium and boron isotopic compositions of olivine in chondrules from carbonaceous and ordinary chondrite meteorites: Implications for the origin of solar 11 B/ 10 B ratio

We report the origin of solar 11 B/ 10 B ratio ~4 remains an open question. It has been thought that a significant portion of boron in the Solar System was derived from continuous spallation nucleosynthesis during interactions between Galactic Cosmic Rays and C—N—O nuclei in the interstellar medium. However, because GCR-produced boron is characterized by 11 B/ 10 B ~2.5, an endmember with 11 B/ 10 B > 4 is required to account for the solar 11 B/ 10 B ratio. Two leading hypotheses for the sources of 11 B-rich components include low energy spallation in the Sun’s parental molecular cloud and the neutrino process during the supernova explosions. In this study, lithium and boron elemental and isotopic compositions of seven porphyritic olivine chondrules and one isolated olivine crystal from four meteorites (Allende, Yamato 81020, Asuka 12236, and QUE 97008) were determined in-situ to help constrain which of the two nucleosynthetic mechanisms has most likely supplied the forming Solar System with extra 11 B. Apparent isotopic variations in Li/Si, B/Si, δ 7 Li and δ 11 B were found in chondrule olivine crystals, but only three chondrules exhibit statistically resolved δ 11 B heterogeneities. Using these three chondrules as a basis for discussion, we evaluated the processes that could potentially cause elemental and isotopic variations of Li and B. We argue that the data can be best understood in the context of condensation of lithium-boron-rich material onto chondrule precursors in (an) initially heterogeneous gaseous reservoir(s), which could be realized if the Solar System derived 11 B-rich components from a supernova or supernovae.

58 GEOSCIENCES↗

Raman Scattering by Crystals of Rare-Earth Hexaborides with Different Isotopes of Boron

Monocrystals of lanthanum hexaboride LaB{sub 6} containing both natural boron and its isotopes {sup 10}B and {sup 11}B have been produced using the solution-melt method. Polyelement hexaboride rare-earths have been grown and the corresponding ceramics have been synthesized for the first time. All these crystals have been studied by means of various techniques, generally using Raman scattering. The Raman spectra attributed to various spectral lines corresponding to nonanalyzable representations have been obtained and interpreted. Frequencies and half-widths of spectral lines have been obtained, the removal of degeneracy and the development of respective splitting of degenerate oscillations induced by defects, mainly by boron isotope inclusions, have been identified. The influence of defects on the Raman spectra has been determined.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultralow-loss polaritons in isotopically pure boron nitride

Conventional optical components are limited to size scales much larger than the wavelength of light, as changes to the amplitude, phase and polarization of the electromagnetic fields are accrued gradually along an optical path. However, advances in nanophotonics have produced ultrathin, so-called ‘flat’ optical components that beget abrupt changes in these properties over distances significantly shorter than the free-space wavelength. Although high optical losses still plague many approaches, phonon polariton (PhP) materials have demonstrated long lifetimes for sub-diffractional modes in comparison to plasmon-polariton-based nanophotonics. We experimentally observe a threefold improvement in polariton lifetime through isotopic enrichment of hexagonal boron nitride (hBN). Commensurate increases in the polariton propagation length are demonstrated via direct imaging of polaritonic standing waves by means of infrared nano-optics. Lastly, our results provide the foundation for a materials-growth-directed approach aimed at realizing the loss control necessary for the development of PhP-based nanophotonic devices.

36 MATERIALS SCIENCE↗

Effects of disorder and isotopic substitution in the specific heat and Raman scattering in LuB{sub 12}

Precision measurements of the specific heat and spectral intensity I({omega}) of Raman scattering for Lu{sup N}B{sub 12} single crystal samples with various boron isotopes (N = 10, 11, nat) have been performed at low and intermediate temperatures. A boson peak in the low-frequency part of the I({omega}) spectrum has been observed for the first time for lutetium dodecaboride at liquid nitrogen temperatures. It has been shown that low-temperature anomalies in the specific heat, along with the features of Raman spectra, can be interpreted in terms of the transition to a cageglass state at T* = 50-70 K, which appears when Lu{sup 3+} ions are displaced from the centrosymmetric position in cavities of a rigid covalent boron sublattice towards the randomly located boron vacancies. The concentrations of various two-level systems that correspond to two types of vibrational clusters with correlation lengths of 12-15 and 18-22 A, respectively, have been estimated. The vibrational density of states of LuB{sub 12} has been calculated from Raman spectra in the model of soft atomic potentials. An approach has been proposed to explain the dielectrization of the properties of the YbB{sub 12} compound at T < T*, as well as the features of the formation of magnetic structures in RB{sub 12} antiferromagnets (R = Tb, Dy, Ho, Er, Tm) and the suppression of superconductivity in LuB{sub 12}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Content of lithium, beryllium, boron, and titanium, and the isotopic composition of lithium, boron, and magnesium in Luna 16 regolith sample

The abundance of the following elements in the L 16-19 No. 118 regolith sample, zone V was determined by isotopic dilution using a mass spectrometer equipped with a scattering ion source: Li -- 9.8, Be -- 1.2, Be -- 2.6, and Ti -- 1.92 percent. For comparison, these same elements were measured in samples of surface material returned by Apollo 11, Apollo 12, and Apollo 14, and in the terrestrial reference standard diabase W-1. The content of Li, Be, and B in the Luna 16 sample is nearly the same as in the Apollo 11 surface material. The surface material returned by Apollo 12 and Apollo 14 contains two to four times more of these elements. However, the abundance ratios of Li, Be, and B are remarkably similar in the surface materials from the four different lunar regions. With respect to basaltic achondrites and especially with respect to chondrites, the lunar basalts are enriched in Li, Be, and B up to 100 times.

Eugster, O.↗

Low-Energy Sputtering Studies of Boron Nitride with Xenon Ions

Sputtering of boron nitride with xenon ions was investigated using secondary ion (SIMS) and secondary neutral (SNMS) mass spectrometry. The ions generated from the ion gun were incident on the target at an angle of 50' with respect to the surface'normal. The energy of ions ranged from 100 eV to 3 keV. A flood electron gun was used to neutralize the positive charge build-up on the target surface. The intensities of sputtered neutral and charged particles, including single atoms, molecules, and clusters, were measured as a function of ion energy. Positive SIMS spectra were dominated by the two boron isotopes whereas BN- and B- were the two major constituents of the negative SIMS spectra. Nitrogen could be detected only in the SNMS spectra. The intensity-energy curves of the sputtered particles were similar in shape. The knees in P-SIMS and SNMS intensity-energy curves appear at around I keV which is significantly higher that 100 to 200 eV energy range at which knees appear in the sputtering of medium and heavy elements by ions of argon and xenon. This difference in the position of the sputter yield knee between boron nitride and heavier targets is due to the reduced ion energy differences. The isotopic composition of secondary ions of boron were measured by bombarding boron nitride with xenon ions at energies ranging from 100 eV to 1.5 keV using a quadrupole mass spectrometer. An ion gun was used to generate the ion beam. A flood electron gun was used to neutralize the positive charge buildup on the target surface. The secondary ion flux was found to be enriched in heavy isotopes at lower incident ion energies. The heavy isotope enrichment was observed to decrease with increasing primary ion energy. Beyond 350 eV, light isotopes were sputtered preferentially with the enrichment increasing to an asymptotic value of 1.27 at 1.5 keV. The trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Ray, P. K.↗

Specific heat of Ce{sub x}La{sub 1-x}B{sub 6} in the low cerium concentration limit (x {<=} 0.03)

The specific heat of high-quality Ce{sub x}La{sub 1-x}B{sub 6} (x = 0, 0.01, 0.03) single crystals is studied in the temperature range 0.4-300 K. LaB{sub 6} samples with various boron isotope compositions ({sup 10}B, {sup 11}B, {sup nat}B) are analyzed to estimate the effect of boron vacancies. The experimental data are used to take into account the electron component correctly under the renormalization of the density of states at T < 8 K, the contribution of the quasi-local vibrational mode of a rare-earth ion with the Einstein temperature {Theta}{sub E} Almost-Equal-To 152 K, the Debye contribution from the rigid cage of boron atoms with the Debye temperature {Theta}{sub D} Almost-Equal-To 1160 K, and the low-temperature Schottky contribution related to the presence of 1.5-2.3% boron vacancies in the rare-earth hexaborides. The detected low-temperature anomalies in the specific heat are shown to be interpreted in terms of the formation of two-level systems with an energy {Delta}E = 92-98 K caused by the displacement of rare-earth ions from their centrosymmetric positions. A scenario of heavy fermion formation that is alternative to the Kondo mechanism is proposed for the systems with a magnetic impurity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗