skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Evidence of gas phase nucleation of nanodiamond in microwave plasma assisted chemical vapor deposition
The mechanism of ballas-like nanodiamond formation still remains elusive, and this work attempts to analyze its formation in the framework of activation energy (Ea) of nanodiamond films grown from a H2/CH4 plasma in a 2.45 GHz chemical vapor deposition system. The Ea was calculated from the Arrhenius equation corresponding to the thickness growth rate using substrate temperature (∼1000−1300 K) in all the calculations. While the calculated values matched with the Ea for nanodiamond formation throughout the literature, these values of ∼10 kcal/mol were lower compared to ∼15–25 kcal/mol for standard single crystal diamond (SCD) formation, concluding thus far that the energetics and processes involved were different. Further, the substrate preparation and sample collection method were modified while keeping the growth parameters constant. Unseeded Si substrate was physically separated from the plasma discharge by a molybdenum disk with a pinhole drilled in it. Small quantity of a sample substance was collected on the substrate. The sample was characterized by electron microscopy and Raman spectroscopy, confirming it to be nanodiamond, thus suggesting that nanodiamond self-nucleated in the plasma and flowed to the substrate that acted as a mere collection plate. It is hypothesized then, if nanodiamond nucleates in gas phase, gas temperature has to be used in the Arrhenius analysis. The Ea values for all the nanodiamond films were re-calculated using the simulated gas temperature (∼1500−2000 K) obtained from a simple H2/CH4 plasma model, giving new values within the range characteristic to SCD formation. Based on these findings, a unified growth mechanism for nanodiamond and SCD is proposed, concluding that the rate-limiting reactions for nanodiamond and SCD formation are the same.  more » « less
Award ID(s):
2333452
PAR ID:
10597362
Author(s) / Creator(s):
;
Publisher / Repository:
American Institute of Physics
Date Published:
Journal Name:
AIP Advances
Volume:
14
Issue:
4
ISSN:
2158-3226
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; (, Journal of Low Temperature Physics)
    We report on electron spin resonance studies of H atoms stabilized in solid H2 films at temperature 0.7 K and in a magnetic field of 4.6 T. The H atoms were produced by bombarding H2 films with 100 eV electrons from a radiofrequency discharge run in the sample cell. We observed a one order of magnitude faster H atom accumulation in the films made of para-H2 gas with a small ortho-H2 concentration (0.2% ortho-H2 ) as compared with those made from normal H2 gas content (75% ortho-H2 ). We also studied the influence of ortho-H2 molecules on spatial diffusion of H atoms in solid H2 films. The spatial diffusion of H atoms in both normal and para-H2 films is faster than the diffusion obtained from the measurement of H atom recombination. The rate of spatial diffusion of H atoms in para-H2 films was slower in comparison with that in the normal H2 films. We discuss possible explanations of these observations. 
    more » « less
  2. (, Biogeosciences)
    null (Ed.)
    Lakes and reservoirs contribute to regional carbon budgets via significant emissions of climate forcing trace gases. Here, for improved modelling, we use 8 years of floating chamber measurements from three small, shallow subarctic lakes (2010–2017, n = 1306) to separate the contribution of physical and biogeochemical processes to the turbulence-driven, diffusion-limited flux of methane (CH4) on daily to multi-year timescales. Correlative data include 9 years of surface water concentration measurements (2009–2017, n = 606), total water column storage (2009–2017, n = 1593) and in situ meteorological observations. We used the latter to compute near surface turbulence based on similarity scaling and then applied the surface renewal model to compute gas transfer velocities. Chamber fluxes averaged 6.9 ± 0.3 mg CH4 m−2 d−1 and gas transfer velocities (k600) averaged 4.0 ± 0.1 cm h−1. Chamber derived gas transfer velocities tracked the power-law wind speed relation of the model. Coefficients for the model and dissipation rates depended on shear production of turbulence, atmospheric stability, and exposure to wind. Fluxes increased with wind speed until daily average values exceeded 6.5 m s−1, at which point emissions were suppressed due to rapid water column degassing reducing the water–air concentration gradient. Arrhenius-type temperature functions of the CH4 flux (Ea‘ = 0.90 ± 0.14 eV) were robust (R2 ≥ 0.93, p < 0.01) and also applied to the surface CH4 concentration (Ea‘ = 0.88 ± 0.09 eV). These results imply that emissions were strongly coupled to production and supply to the water column. Spectral analysis indicated that on timescales shorter than a month, emissions were driven by wind shear whereas on longer timescales variations in water temperature governed the flux. Long-term monitoring efforts are essential to identify distinct functional relations that govern flux variability on timescales of weather and climate change. 
    more » « less
  3. ; ; ; ; ; (, Catalysts)
    null (Ed.)
    In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170 °C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170 °C and a sub-Arrhenius relation was elucidated with activation energy being dependent on temperature, and ranging from 10.2–51.8 kJ/mol in the temperature range investigated. Internal and external mass transfer were investigated through evaluating the Weisz–Prater criterion and the effect of varying stirring rate on the reaction rate, respectively. There were no internal or external mass transfer limitations present in the reaction. 
    more » « less
  4. ; ; (, C)
    In this paper, carbon thin films were grown using the plasma-enhanced atomic layer deposition (PE-ALD). Methane (CH4) was used as the carbon precursor to grow the carbon thin film. The grown film was analyzed by the high-resolution transmission electron micrograph (TEM), X-ray photoelectron spectroscopy (XPS) analysis, and Raman spectrum analysis. The analyses show that the PE-ALD-grown carbon film has an amorphous structure. It was found that the existence of defective sites (nanoscale holes or cracks) on the substrate of copper foil could facilitate the formation of nanolayered carbon films. The mechanism for the formation of nanolayered carbon film in the nanoscale holes was discussed. This finding could be used for the controlled growth of nanolayered carbon films or other two-dimensional nanomaterials while combining with modern nanopatterning techniques. 
    more » « less
  5. ; ; ; ; ; ; ; (, The ISME Journal)
    Abstract The size and biogeochemical impact of the subseafloor biosphere in oceanic crust remain largely unknown due to sampling limitations. We used reactive transport modeling to estimate the size of the subseafloor methanogen population, volume of crust occupied, fluid residence time, and nature of the subsurface mixing zone for two low-temperature hydrothermal vents at Axial Seamount. Monod CH4 production kinetics based on chemostat H2 availability and batch-culture Arrhenius growth kinetics for the hyperthermophile Methanocaldococcus jannaschii and thermophile Methanothermococcus thermolithotrophicus were used to develop and parameterize a reactive transport model, which was constrained by field measurements of H2, CH4, and metagenome methanogen concentration estimates in 20–40 °C hydrothermal fluids. Model results showed that hyperthermophilic methanogens dominate in systems where a narrow flow path geometry is maintained, while thermophilic methanogens dominate in systems where the flow geometry expands. At Axial Seamount, the residence time of fluid below the surface was 29–33 h. Only 1011 methanogenic cells occupying 1.8–18 m3 of ocean crust per m2 of vent seafloor area were needed to produce the observed CH4 anomalies. We show that variations in local geology at diffuse vents can create fluid flow paths that are stable over space and time, harboring persistent and distinct microbial communities. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email