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Chen, Ping

Publications and source records attributed to Chen, Ping.

At least 19 records

Effect of 60 Co Irradiation on Boehmite Dissolution in Caustic Solutions

Here, in this work, we examine how radiation impacts the dissolution behavior of boehmite by subjecting dry nanoparticles of different sizes to 60 Co γ radiation and subsequently analyzing their dissolution behavior in caustic solutions as a function of temperature. The measured kinetics show that irradiation with an amount 228.24 Mrad significantly slows the dissolution rate, particularly for smaller sizes at lower temperatures. Specifically, the temperature-dependent dissolution rates of irradiated 20 nm boehmite versus pristine material in 3 M NaOH solutions were several times lower (e.g., rate constant of 0.026 vs 0.075 h –1 at 60 °C), with an apparent activation energy 40 kJ mol –1 higher. Although various imaging techniques and X-ray diffraction measurements consistently revealed no obvious differences between pristine and irradiated samples, after irradiation significant binding energy shifts were detected in the X-ray photoelectron Spectroscopy peaks of Al 2p and O 1s, and a change in their relative intensities indicated a lower O/Al ratio. This suggests that γ-irradiation may stabilize boehmite particle surfaces by driving their chemistry and structure toward more stable aluminum oxide forms. This finding may help explain slower dissolution rates of boehmite in nuclear waste and may be useful for the development of more robust predictive models and effective strategies for waste processing.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Global rare earth element resources: A concise review

Deposits enriched in rare earth elements (REEs) are abundant and diverse in mineralogy, but those of current economic value have extremely limited geographic distribution. Due to rapidly increasing demand and concerns about supply chain security, new and improved methods of prospecting, beneficiation, separation, purification, and recycling are needed. By overviewing the types and geographic distribution of REE reserves globally, their petrogenesis and major mineralogic assemblages, this review aims to provide a foundation for posing new directions for research and development in these areas. In conclusion, our review also seeks to provide a concise summary of important background information that is accessible to researchers from a variety of disciplines who are seeking to engage in this rapidly expanding field.

58 GEOSCIENCES↗

Tailoring Solvation Solvent in Localized High-Concentration Electrolytes for Lithium||Sulfurized Polyacrylonitrile

Sulfurized polyacrylonitrile (SPAN) is a promising cathode material for lithium-sulfur (Li-S) batteries due to its significantly reduced polysulfide (PS) dissolution compared to the elemental S cathode. Although conventional carbonate-based electrolytes is stable with SPAN electrodes, it is less stable with Li metal anode (LMA). Recently, localized high-concentration electrolytes (LHCEs) have been developed to improve the stability of LMA. Here, we report a new strategy to further improve the performance of LI||SPAN batteries by replacing the conventional solvating solvent 1,2-dimethoxyethane (DME) in the LHCE with a new solvating solvent, 1,2-diethoxyethane (DEE), the new LHCEs exhibits less reactivity against Li 2 S 2 , alleviates PS dissolution, forms a better cathode-electrolyte interphase layer on the SPAN, and enhances structure reversibility even at elevated temperature (ET, 45°C). With the same salt and diluent as in other LHCEs, the LHCE with DEE leads to better performance in Li||SPAN batteries (with 82.9% capacity retention after 300 cycles at ET), preservation of SPAN cathode structure, and suppression of the volume change of LMA. The similar strategy on tailoring the solvating solvents in LHCEs can also be used in other rechargeable batteries to improve their performances.

1,2-diethoxyethane↗

Effect of Impurities on Radical Formation in Gibbsite Radiolysis

The generation and stabilization of gamma radiation-induced hydrogen atoms in gibbsite (Al(OH)3) nanoplates is directly related to the nature of residual ions from synthetic precursors used, whether nitrates or chlorides. The concentration of hydrogen atoms trapped in the interstitial layers of gibbsite is lower and decays faster in comparison to boehmite (AlOOH), which could affect the waste management of these materials.

Hlushko, Hannah↗

Incorporation of rare earth elements $\text{Sc}$, $\text{Y}$ and $\text{La}$ into gibbsite

Rare earth elements (REE) are increasingly critical resources in technological applications, but the current understanding of their separation by uptake into minerals remains limited. We examined the adsorption and solubilization of scandium (Sc), yttrium (Y), and lanthanum (La) into aluminum hydroxide (gibbsite, Al(OH) 3 ). Based on spectroscopic investigations such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and time of flight-secondary ion mass spectrometry (ToF-SIMS), only Sc exhibited favorable incorporation and adsorption (0.66 and 0.06 atom%, respectively). Analysis of solid state 45 Sc magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) indicated that Sc exhibits an octahedral coordination consistent with isolated substitutions for Al in the gibbsite structure, leading to a increase in lattice constants detectable by X-ray diffraction. Density functional theory (DFT) calculations reinforced this interpretation by reproducing the detected structural distortion as well as demonstrating the relatively favorable energetic basis for Sc incorporation into gibbsite by substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser-Induced Photoreduction of Iron(III) Oxide Nanoparticles Enhanced by the Presence of Organic Chromophores

Light-induced electron transfer between chromophoric organic matter and Fe(III)-oxides lies at the heart of aqueous Fe(II) fluxes in the photic zone of natural systems. Understanding this photoreductive dissolution process is also essential for developing water purification techniques based on this class of materials. Previously, optical transient absorption spectroscopy (TAS) measurements revealed that sub-picosecond relaxation times of photo-excited rhodamine B (RhB) dye increased when sorbed onto hematite nanoparticles (HNPs), consistent with electron transfer to the oxide. Here, in the present study, we exploit time-resolved X-ray absorption spectroscopy (XAS) at the Fe K-edge to follow the Fe oxidation state for this same process to (i) confirm that RhB photoexcitation leads to interfacial electron transfer and Fe reduction; and (ii) quantify the lifetime of injected electrons as a function of solution conditions. Regardless of RhB dye availability and pH, direct band gap photoexcitation of HNPs yields an Fe(II)-like small polaronic absorption signature with a lifetime of ~ 1 ns, an order of magnitude longer than previously reported. However, when RhB is present at low pH under conditions where dye favorably interacts with the positively charged hematite surface, a second relaxation process approaching microsecond timescales is observed that likely represents back-reaction with the photoexcited adsorbed dye. At pH above neutral, the efficiency of the interfacial electron transfer is diminished by weaker interaction between sorbed dye and particle surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Ionizing Radiation on the Thermodynamic Stability of Boehmite and Gibbsite

Here, in this study, we examined the effect of gamma radiation on the stabilities of aluminum hydroxide (gibbsite) and aluminum oxyhydroxide (boehmite) nanoparticles in relation to their thermal decomposition. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images revealed no significant differences in mineral components or morphology before and after radiation. However, thermogravimetric and differential scanning calorimetry (TGA/DSC) analyses showed that both boehmite and gibbsite nanoparticles experienced decreased mass loss following irradiation. Raman and attenuated total reflection-Fourier transfer infrared (ATR-FTIR) spectra indicated that a fraction of the hydroxyl content in both cases was selectively cleaved by radiation, primarily at the particle surfaces. Quantitative analyses of thermal mass loss behavior demonstrated that irradiated boehmite and gibbsite nanoparticles had higher activation energies than their pristine counterparts, with the extent of the increase dependent on the total dose. Taken together, these findings suggest that exposure to a sufficient dose of ionizing radiation alters these materials such that they are less prone to decomposition by dehydration. This increased stability may be due to the decreased hydrous nature of the samples after radiation exposure, which was supported by further high temperature drop calorimetry. Additionally, a radiation-induced amorphous phase on the nanoparticle surfaces appears to have a permanent and positive influence on their thermodynamic stabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facet-dependent dispersion and aggregation of aqueous hematite nanoparticles

Nanoparticle aggregates in solution controls surface reactivity and function. Complete dispersion often requires additive sorbents to impart a net repulsive interaction between particles. Facet engineering of nanocrystals offers an alternative approach to produce monodisperse suspensions simply based on facet-specific interaction with solvent molecules. Here, we measure the dispersion/aggregation of three morphologies of hematite (α-Fe 2 O 3 ) nanoparticles in varied aqueous solutions using ex situ electron microscopy and in situ small-angle x-ray scattering. We demonstrate a unique tendency of (104) hematite nanoparticles to maintain a monodisperse state across a wide range of solution conditions not observed with (001)- and (116)-dominated particles. Density functional theory calculations reveal an inert, densely hydrogen-bonded first water layer on the (104) facet that favors interparticle dispersion. Results validate the notion that nanoparticle dispersions can be controlled through morphology for specific solvents, which may help in the development of various nanoparticle applications that rely on their interfacial area to be highly accessible in stable suspensions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-house synthesized poly(ether ether ketone) ionenes. I. ToF-SIMS spectra in the positive ion mode

Static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for acquiring the high-resolution surface spectra of four types of synthesized imidazolium ionene membranes. These novel membranes have aromatic ether–ketone–ether linkages inspired by poly(ether ether ketone) (PEEK). The PEEK-ionenes synthesized for this study have imidazolium cations placed in the polymeric backbone with bistriflimide [Tf 2 N]- counterions. The attention given to synthetically modified PEEK derivatives, such as PEEK-ionenes, is considerable due to their ability to selectively capture CO 2 molecules and other light gases. Therefore, it is important to characterize the surface of these synthesized novel PEEK-ionenes. In this work, characteristic and unique peaks were identified in the positive spectra of each sample. The differences in mass spectra among the samples provide insights for optimizing or fine-tuning the PEEK-ionenes synthesis to achieve a high-performance CO 2 separation membrane with enhanced permeability, selectivity, and mechanical stability. The SIMS spectra and identified characteristic peaks of these synthesized ionenes will serve as a reference in the positive mode, complementing the corresponding spectra reported in the negative ion mode (Paper II).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-house synthesized poly(ether ether ketone) ionenes. II. ToF-SIMS spectra in the negative ion mode

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to analyze poly(ether ether ketone) (PEEK) based membranes. PEEK membranes have been shown to be effective in the separation of CO 2 from flue gases (post-combustion technique). The PEEK membranes were synthesized using novel aromatic ether-ketone linkages inspired by PEEK with polymeric backbone bistriflimide [Tf2N]− counterions. One of the keys to advancing this technology is developing membranes that are selective and permeable toward CO 2 , in which PEEK based membranes have been shown to be. Furthermore, the compatibility between various water lean solvents also needs to be investigated. Surface analytical techniques such as x-ray photoelectron spectroscopy and ToF-SIMS are useful for investigating chemical changes between membranes. Herein, we present ToF-SIMS data obtained in the negative ion mode for four different PEEK membranes designed for use in CO 2 capture systems. Positive ion mode spectra are reported in Paper I.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel principal component analysis tool based on python for analysis of complex spectra of time-of-flight secondary ion mass spectrometry

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful surface analysis tool, which can simultaneously provide elemental, isotopic, and molecular information with part per million (ppm) sensitivity. However, each spectrum may be composed of hundreds of ion signals, which makes the spectra data complex. Principal component analysis (PCA) is a multivariate analysis technique that has been widely used to figure out the variances among samples in ToF-SIMS spectra data analysis and is showing great success in the explanation of complex ToF-SIMS spectra. So far, several software tools have been developed for PCA of ToF-SIMS spectra; however, none of them are freely available. Such a situation leads to some difficulties in extending applications of PCA to various research fields. More importantly, it has long been challenging for common researchers to understand PCA plots and extract chemical differences among samples. In this work, we developed a new and flexible software tool (named “advanced spectra pca toolbox”) based on python for PCA of complex ToF-SIMS spectra along with an easy-to-read manual. It can generate data analysis reports automatically to explain chemical differences among samples, allowing less experienced researchers to easily understand tricky PCA results. Moreover, it is expandable and compatible with artificial intelligence/machine learning functions. Pure goethite and different lignin adsorbed goethite samples were used as a model system to demonstrate our new software tool, proving that our software tool can be readily used in complex spectra data processing. Our new software tool is open-source, convenient, flexible, and expandable. We expect this open-source tool will benefit the ToF-SIMS community.

47 OTHER INSTRUMENTATION↗

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions

Understanding the dissolution of boehmite in highly alkaline solutions is important to the processing of the complex nuclear wastes stored at the Hanford (WA) and Savannah River (SC) sites. Here, we report the adsorption of model carboxylate anions on boehmite nanoplates in alkaline solutions and their effects on subsequent boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate at pH 13 at room temperature was significant and remained so through a linear decrease to 3 M NaOH conditions with no evidence for the appearance of new phases. Modeling of the adsorption data and rate were consistent with the formation of outer-sphere surface complexes. By using these conditions to preload the boehmite nanoplates with oxalate, and separately acetate, we measured and compared their dissolution behavior at 80 °C and observed a clear suppression of the dissolution rate for the case of adsorbed oxalate by 23% and for adsorbed acetate by 10% compared to pure solids. Ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. In conclusion, we nonetheless conclude that pre-adsorbed carboxylate anions, even as nominally weakly bound outer-sphere complexes, can persist on the surface through highly alkaline conditions, decreasing the density of dissolution-active sites and thereby adding an extrinsic control on the dissolution rate.

Adsorption kinetics↗

A quasi-permeable barrier in the equatorial lower stratosphere

Analyses of global isentropic maps of potential vorticity from the United Kingdom Meteorological Office (UKMO) data assimilation system reveal that there is a region of strong meridional potential vorticity (PV) gradients in the equatorial lower stratosphere. A semi-Lagrangian tracer transport model is used to show that this region of strong PV gradients acts as a quasipermeable barrier to cross-equator mass exchange on isentropic surfaces.

Chen, Ping↗

Mixing by barotropic instability in a nonlinear model

A global, nonlinear, equivalent barotropic model is used to study the isentropic mixing of passive tracers by barotropic instability. Basic states are analytical zonal-mean jets representative of the zonal-mean flow in the upper stratosphere, where the observed 4-day wave is thought to be a result of barotropic, and possibly baroclinic, instability. As is known from previous studies, the phase speed and growth rate of the unstable waves is fairly sensitive to the shape of the zonal-mean jet; and the dominant wave mode at saturation is not necessarily the fastest growing mode; but the unstable modes share many features of the observed 4-day wave. Lagrangian trajectories computed from model winds are used to characterize the mixing by the flow. For profiles with both midlatitude and polar modes, mixing is stronger in midlatitude than inside the vortex; but there is little exchange of air across the vortex boundary. There is a minimum in the Lyapunov exponents of the flow and the particle dispersion at the jet maximum. For profiles with only polar unstable modes, there is weak mixing inside the vortex, no mixing outside the vortex, and no exchange of air across the vortex boundary. These results support the theoretical arguments that, whether wave disturbances are generated by local instability or propagate from other regions, the mixing properties of the total flow are determined by the locations of the wave critical lines and that strong gradients of potential vorticity are very resistant to mixing.

Bowman, Kenneth P.↗

The permeability of the Antarctic vortex edge

Mixing and cross-vortex mass transport along isentropic surfaces in the lower stratosphere are investigated with a 'contour advection' technique and a semi-Lagrangian transport model for the Antarctic winter of 1993 using analyzed winds from the United Kingdom Meteorological Office data assimilation system. Results from the 'contour advection' technique show that at the vortex edge there exists a potential vorticity (PV) contour that has the smallest lengthening rate. This PV contour is referred to as the 'line of separation' because it essentially separates the inner and outer vortex. The average e-folding time for the lengthening of the 'line of separation' increases monotonically with altitude, ranging from about 7 days on the 350 K isentropic surface to about 105 days on the 500 K isentropic surface. The results also suggest the existence of a transition layer around the 400 K isentropic surface, above which the vortex is nearly completely isolated from the midlatitudes and below which the vortex is less isolated. Results from a semi-Lagrangian transport model with an idealized tracer initially inside the inner vortex show that at 425 K and above virtually no tracer is transported out of the vortex during a 40-day integration starting from July 21, 1993. At 400 K and below a small amount of the tracer is transported out of the vortex while the bulk of the tracer remains confined within the inner vortex.

Chen, Ping↗

Isentropic mass exchange between the Tropics and extratropics in the stratosphere

The isentropic mass exchange between the Tropics and extratropics in the stratosphere is investigated with a semi-Lagrangian transport model for the periods from 1 June to 31 October 1992 and from 1 December 1992 to 30 April 1993 using winds from the U.K. Meteorological Office data assimilation system. Calculations with an idealized, initially zonally symmetric tracer show that in the middle and upper stratosphere the bulk of tropical air is transported into the midlatitudes of the winter hemisphere although there exist quasi-permeable barriers in the subtropics. The transport takes place in the form of planetary-scale 'tongues' of material that are drawn poleward in association with the episodic amplification of planetary-scale waves in high latitudes of the winter hemisphere. Once air of tropical origin is transported to the midlatitudes it is irreversibly mixed with the midlatitude air in the 'surf zone.' Air of tropical origin can, however, hardly penetrate into the interior of the winter polar vortex until the breakdown of the vortex. Transport of tropical air into the midlatitudes of the summer hemisphere is strongly inhibited. In the lower stratosphere, tropical air is transported into the northern and southern midlatitudes. During the period from 1 June to 31 October 1992, the amount of tropical air transported into the Northern Hemisphere is, however, much smaller than that transported into the Southern Hemisphere, and there exist strong gradients in the tracer field in the equatorial region, indicating that there is a quasi-permeable barrier to cross-equator mass exchange. During the period from 1 December 1992 to 30 April 1993, on the other hand, roughly the same amounts of tropical air are transported into the Southern Hemisphere, and there exist strong gradients in the tracer field in the equatorial region, indicating that there is a quasi-permeable barrier to cross-equator mass exchange. During the period from 1 December 1992 to 30 April 1993, on the other hand, roughly the same amounts of tropical air are transported into the northern midlatitudes and into the southern midlatitudes, and there exist no significant transport barriers in the equatorial area.

Chen, Ping↗

Turbulent mixing noise from supersonic jets

There is now a substantial body of theoretical and experimental evidence that the dominant part of the turbulent noise of supersonic jets is generated directly by the large turbulence structures/instability waves of the jet flow. Earlier, Tam and Burton provided a description of the physical mechanism by which supersonically traveling instability waves can generate sound efficiently. They used the method of matched asymptotic expansions to construct an instability wave solution which is valid in the far field. The present work is an extension of the theory of Tam and Burton. It is argued that the instability wave spectrum of the jet may be regarded as generated by stochastic white noise excitation at the nozzle lip region. The reason why the excitation has white noise characteristics is that near the nozzle lip region the flow in the jet mixing layer has no intrinsic length and time scales. The present stochastic wave model theory of supersonic jet noise contains a single unknown multiplicative constant. Comparisons between the calculated noise directivities at selected Strouhal numbers and experimental measurements of a Mach 2 jet at different jet temperatures have been carried out. Favorable agreements are found.

Tam, Christopher K. W.↗

Quasi-horizontal transport and mixing in the Antarctic stratosphre

The quasi-horizontal transport and mixing properties of the Antarctic stratosphere are investigated with a simi-Lagrangian transport model and a 'contour advection' technique for the winter and spring of 1992 using analyzed winds from the United Kingdom Meteorological Office data assimiliation system. Transport calculations show that passive tracers are well mixed inside the polar vortex as well as in the midlatitude 'surf zone.' A the vortex edge, strong radial gradients in the tracer fields are well preserved, and their evolutions follow that of the potential vorticity until some time after the breakdown of the polar vortex. In the middle stratosphere there is little tracer exchange across the vortex edge in August and September. Some vortex air is eroded into the surf zone in filamentary form in October, and very strong exchange of air occurs between high and middle latitudes in November. In the lower stratosphere the vortex is not so isolated from the midlatitudes as in the middle stratosphere, and there is more mass exchange across the vortex edge. Calculations of the lengthening of material contours using the contour advection technique show that in the middle stratosphere, strong stirring (i.e., stretching and folding of material elements) occurs in the inner vortex, while the strongest stirring occurs in the midlatitude surf zone and the weakest occurs at the vortex edge. In the lower strtosphere, strong stirring occurs in the inner vortex. Stirring is moderate at the vortex edge and in the midlatitudes.

Chen, Ping↗