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At least 1,459 records · Page 81

Inhibitive formation of nanocavities by introduction of Si atoms in Ge nanocrystals produced by ion implantation

Germanium nanocrystals (Ge-nc) were successfully synthesized by co-implantation of Si and Ge ions into a SiO{sub 2} film thermally grown on (100) Si substrate and fused silica (pure SiO{sub 2}), respectively, followed by subsequent annealing at 1150 °C for 1 h. Transmission electron microscopy (TEM) examinations show that nanocavities only exist in the fused silica sample but not in the SiO{sub 2} film on a Si substrate. From the analysis of the high-resolution TEM images and electron energy-loss spectroscopy spectra, it is revealed that the absence of nanocavities in the SiO{sub 2} film/Si substrate is attributed to the presence of Si atoms inside the formed Ge-nc. Because the energy of Si-Ge bonds (301 kJ·mol{sup −1}) are greater than that of Ge-Ge bonds (264 kJ·mol{sup −1}), the introduction of the Si-Ge bonds inside the Ge-nc can inhibit the diffusion of Ge from the Ge-nc during the annealing process. However, for the fused silica sample, no crystalline Si-Ge bonds are detected within the Ge-nc, where strong Ge outdiffusion effects produce a great number of nanocavities. Our results can shed light on the formation mechanism of nanocavities and provide a good way to avoid nanocavities during the process of ion implantation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A General Optimality Conditions for Stochastic Control Problems of Jump Diffusions

We consider a stochastic control problem where the system is governed by a non linear stochastic differential equation with jumps. The control is allowed to enter into both diffusion and jump terms. By only using the first order expansion and the associated adjoint equation, we establish necessary as well as sufficient optimality conditions of controls for relaxed controls, who are a measure-valued processes.

97 MATHEMATICS AND COMPUTING↗

First-principles investigation of native interstitial diffusion in Cr2O3

First principles density functional theory (DFT) investigation of native interstitials and the associated self-diffusion mechanisms in a-Cr2O3 reveals that interstitials are more mobile than vacancies of corresponding species. Cr interstitials occupy the unoccupied Cr sublattice sites that are octahedrally coordinated by 6 O atoms, and O interstitials form a dumbbell configuration orientated along the [221] direction (diagonal) of the corundum lattice. Calculations predict that neutral O interstitials are predominant in O-rich conditions and Cr interstitials in +2 and +1 charge states are the dominant interstitial defects in Cr-rich conditions. Similar to that of the vacancies, the charge transition levels of both O and Cr interstitials are located deep within the bandgap. Transport calculations reveal a rich variety of interstitial diffusion mechanisms that are species, charge, and orientation dependent. Cr interstitials diffuse preferably along the diagonal of corundum lattice in a two step process via an intermediate defect complex comprising a Cr interstitial and an adjacent Cr Frenkel defect in the neighboring Cr bilayer. This mechanism is similar to that of the vacancy mediated Cr diffusion along the c-axis with intermediate Cr vacancy and Cr Frenkel defect combination. In contrast, O interstitials diffuse via bond switching mechanism. O interstitials in -1 and -2 charge states have very high mobility compared to neutral O interstitials.

Medasani, Bharat K.↗

Integrated Strategies for Overcoming Resolution Limits in Electron Beam Lithography of Chemically Amplified Resists

Electron beam lithography (EBL) of chemically amplified resists (CARs) faces fundamental challenges, including stochastic electron scattering and acid diffusion, that limit resolution and reproducibility. Using SU-8 as a model CAR, this study systematically investigated complementary strategies to address these challenges, combining multipass exposure, proximity effect correction (PEC) with midrange correction factors, base quencher incorporation, and post-exposure bake (PEB) suppression. Monte Carlo simulations and calibrated PEC modeling revealed that extending the point spread function to include a midrange scattering component significantly improved critical dimension (CD) control across varying pattern densities, correcting deviations that conventional two-term PEC failed to capture. Multipass exposure, particularly 4-pass writing with a 25% offset, redistributed the dose to average stochastic beam and scattering fluctuations, reducing line-width roughness by more than 50% and yielding more uniform nanoscale features. Photoacid confinement was investigated by adding urea as a base quencher, which successfully reduced acid diffusion but introduced substantial sensitivity penalties without improving ultimate resolution or Z-factor performance, underscoring the trade-offs of chemical versus physical confinement. Suppressing PEB most directly minimized acid diffusion, resulting in improved Z-factors and reproducible 30 nm half-pitch dense line/space patterns. Overall, these results demonstrated that PEC with midrange correction, multipass strategies, quencher additives, and PEB-free processing addresses different aspects of the EBL process window and that their integration provides a comprehensive framework for managing stochastic scattering, diffusion, and chemical amplification effects. This framework advances dense nanoscale patterning in CARs and establishes guiding principles for optimizing resist design and process strategies in high-resolution EBL and potentially other advanced lithographies, such as extreme ultraviolet (EUV) lithography.

36 MATERIALS SCIENCE↗

Deformation Mechanisms and Formability Window for As-Cast Mg-6Al-2Ca-1Sn-0.3Sr Alloy (MRI 230D)

The hot deformation characteristics of MRI 230D alloy have been evaluated in the temperature range 260-500 °C and strain rate range 0.0003-10 s{sup −1}, on the basis of processing map. The processing map exhibited two domains in the ranges: (1) 300-370 °C and 0.0003-0.001 s{sup −1} and (2) 370-480 °C and 0.0003-0.1 s{sup −1}. Dynamic recrystallization occurs in the both domains with basal slip dominating in the first domain along with climb as recovery process and second-order pyramidal slip dominating in the second with the recovery by cross-slip. In Domains (1) and (2), the apparent activation energy values estimated using the kinetic rate equation are 143 and 206 kJ/mole, respectively, the first one being close to that for lattice self-diffusion confirming climb. It is recommended that the alloy is best processed at 450 °C and strain rates less than 0.1 s{sup −1}, where non-basal slip and cross-slip occur extensively to impart excellent workability. The alloy exhibits flow instability in the form of adiabatic shear band formation and flow localization at lower temperatures and higher strain rates. Forging of a cup-shaped component was performed under various conditions, and the results validated the predictions of the processing map on the workability domains as well as the instability regimes.

36 MATERIALS SCIENCE↗

Dynamic re-equilibration controlled multi-step transformations in (Mn, Fe) 2 (P, Si) alloys

In (Mn, Fe) 2 (P, Si) alloys crystallographic first-order phase transformations enable strong coupling of magnetic and entropic properties, potentially leading to high-efficiency energy generation and refrigeration applications. Although hysteresis losses that limit these applications can be reduced through careful control of alloy composition, compositional tuning can also unfavorably influence transformation temperatures and magnetocaloric coupling strength. Hence, exploration of additional processing variables enabling independent control of transformation properties is crucial. In this work, we investigate the role of thermal history as an additional processing variable, exploiting thermally-activated mechanisms to control properties of non-diffusive transformations in (Mn, Fe) 2 (P, Si) alloys. In so doing, we report an unusual transformation-splitting phenomenon following annealing at intermediate times, where a single well-defined magneto-structural transformation evolves towards a multi-step transformation with individual steps occurring at multiple distinct temperatures. Here, on longer annealing at the same temperatures, single-step transformation behavior is recovered. Through additional magnetic and crystallographic characterization, we show that the thermal history-controlled multi-step behavior results from sluggish thermally-activated diffusion. The two-step transformation corresponds to non-equilibrium bimodal composition distributions in the transforming phase, and these develop through a dynamic re-equilibration process as the alloy passes relatively slowly between different thermal equilibria. Together, these results suggest that thermal history primarily controls the transformation properties of (Mn, Fe) 2 (P, Si) alloys indirectly through the composition of one or more transforming phases. Additional investigations are needed to develop thermal history processing for decoupling hysteresis control from other transformation properties.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Effect of sintering temperature on adhesion of spray-on piezoelectric transducers

Conventionally sol-gel spray-on transducers require a high-temperature (> 700 ◦C) sintering process; however, this process can affect the microstructure of the substrate material. For mechanical elbows and valves utilized for fluid transport in the energy sector, the components are designed to have a specific microstructure, and deviations from these specifications can create weak points in the system. For this reason it is important to investigate how the temperature of the deposition process affects the substrate. This paper investigates the effect of high-temperature and low-temperature (< 150 ◦C) processing conditions on the surface composition of the substrate. Furthermore, the resultant transducers from high- and low-temperature fabrication processes are compared to determine if a low-temperature processing method is feasible. For these studies a sol-gel spray-on process is employed to deposit piezoelectric ceramics onto a stainless-steel 316L substrate. Energy-dispersive X-ray spectroscopy is utilized to determine the composition of the substrate surface before and after transducer deposition. Results indicate that the high-temperature processing conditions may alter the surface composition of the metal due to a diffusion of the metal into the ceramic, which results in a metal surface that is bonded to the ceramic. Furthermore, it is shown that low-temperature processing of spray-on transducers is a viable method for transducer fabrication where the resultant transducers meet the industry minimum requirement of 30 dB signalto-noise ratio. In parallel simulation calculations, finite-element method (FEM) studies were performed to model the adhesive strength of the low-temperature processed transducer to the substrate surface. Comparisons between the simulations and experiments suggest that the bond strength is much greater than the commercial gel bonds and closer to hardened epoxy glue bonds. These results indicate that spray-on transducers fabricated under lowtemperature processing conditions are a viable solution for leave-in-place monitoring of structures.

M. Sinding, Kyle↗

Diffuse Reflectance Spectroscopy and Principal Component Analysis to Retrospectively Determine Production History of Plutonium Dioxide

Diffuse reflectance spectroscopy measurements in the shortwave infrared (930–1600 nm) spectral region were acquired for Pu 2 (C 2 O 4 ) 3 •9H 2 O and its thermal decomposition product, PuO 2 . We analyzed a total of eight PuO 2 samples that were produced at different calcination temperatures (300, 350, 450, 525, 600, 675, 750, and 900 °C). Our goal was to identify spectroscopic fingerprints that could be used to gain retrospective information regarding the production parameters of these important nuclear compounds. The diffuse reflectance spectrum of Pu 2 (C 2 O 4 ) 3 •9H 2 O features several broad bands that currently preclude detailed analysis. However, all PuO 2 samples produced relatively sharp spectral features that got sharper and more intense for samples that were produced at higher calcination temperatures. The electronic band observed at 1433 nm in the diffuse reflectance spectra of PuO 2 was found to be a sensitive indicator of crystallinity; a result that is corroborated by ancillary Raman spectroscopy measurements. Principal component analysis of diffuse reflectance spectra was able to clearly rank and categorize PuO 2 samples based on the calcination temperature that was employed during their production. Thus, we show herein that important retrospective information pertaining to the process history of PuO 2 can be gained through the relatively simplistic combination of diffuse reflectance spectroscopy and principal component analysis. This discovery presents a new method for determining the provenance and process history of PuO 2 and should have an impact in the fields of nuclear forensics and nuclear nonproliferation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A stochastic mechanism of electron heating

Due to Landau resonant interaction with lower hybrid waves in the lower hybrid current drive scheme part of electrons are accelerated and, as a result of this, a tail of energetic electrons is formed on the electron distribution function. The same situation takes place in the problem of type III radio bursts when the suprathermal burst electrons acquire a plateau distribution due to excitation of plasma waves in the solar wind plasma. These distributions are unstable with respect to the cyclotron excitation of waves at anomalous Doppler resonance ('fan' instability). In this case, the tail electrons interact simultaneously with both (i) waves that accelerate or decelerate them (Cerenkov resonance) and (ii) waves excited in the process of the fan instability that led to their pitch angle diffusion. Because velocity diffusion lines of electrons formed due to heir interaction with each type of waves intersect, this interaction can lead not only to pitch angle diffusion but also to heating of electrons mainly in perpendicular direction. We investigated this mechanism of electron heating and studied the temporal evolution of the electron temperature and the energy of excited waves. Our results show significant enhancement of the electron perpendicular temperature T{sub Up-Tack} due to this stochastic heating mechanism.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Multidimensional visualization of the dynamic evolution of Li metal via in situ/operando methods

The growing demands for high-energy density electrical energy storage devices stimulate the coupling of conversion-type cathodes and lithium (Li) metal anodes. While promising, the use of these “Li-free” cathodes brings new challenges to the Li anode interface, as Li needs to be dissolved first during cell operation. In this study, we have achieved a direct visualization and comprehensive analysis of the dynamic evolution of the Li interface. The critical metrics of the interfacial resistance, Li growth, and solid electrolyte interface (SEI) distribution during the initial dissolution/deposition processes were systematically investigated by employing multidimensional analysis methods. They include three-electrode impedance tests, in situ atomic force microscopy, scanning electrochemical microscopy, and cryogenic scanning transmission electron microscopy. The high-resolution imaging and real-time observations show that a loose, diffuse, and unevenly distributed SEI is formed during the initial dissolution process. This leads to the dramatically fast growth of Li during the subsequent deposition, deviating from Fick’s law, which exacerbates the interfacial impedance. The compactness of the interfacial structure and enrichment of electrolyte species at the surface during the initial deposition play critical roles in the long-term stability of Li anodes, as revealed by operando confocal Raman spectroscopic mapping. In conclusion, our observations relate to ion transfer, morphological and structural evolution, and Li (de)solvation at Li interfaces, revealing the underlying pathways influenced by the initial dissolution process, which promotes a reconsideration of anode investigations and effective protection strategies.

25 ENERGY STORAGE↗

Mass transfer in catalytic depolymerization: External effectiveness factors and serendipitous processivity in stagnant and stirred melts

Several heterogeneous catalysts are being developed to recycle plastics. Most operate in viscous polymer melts, where external mass transfer effects could limit the supply of co-reactants to active sites. External mass transfer can also impede the diffusion of long chain products away from the catalyst after each cut. Product egress limitations could potentially confer unintentional processivity to catalyst operation, i.e. a tendency for the catalyst to repeatedly cut the same chain after an initial encounter. We formulate reaction–diffusion equations to quantify mass transfer effects on the co-reactant transport to the catalyst and the degree of serendipitous processivity. Results are developed for catalysts in stagnant or stirred melts, with simple expressions involving Damkohler, Peclet, and Sherwood numbers, i.e. dimensionless combinations of rate constants, catalyst particle size, polymer diffusivities, and shear rates (where applicable). In conclusion, we estimate the impact of these effects for a spherical core–shell catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

RuO 2 nanoparticles supported on MnO 2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery

RuO2 nanoparticles supported on MnO2 nanorods (denoted as np-RuO2/nr-MnO2) were synthesized via a two-step hydrothermal reaction. SEM and TEM images both illustrated that RuO2 nanoparticles are well dispersed on the surface of MnO2 nanorods in the as-prepared np-RuO2/nr-MnO2 material. Electrochemical results demonstrated that the np-RuO2/nr-MnO2 as oxygen cathode of Li-O-2 batteries could maintain a reversible capacity of 500 mA h g(-1) within 75 cycles at a rate of 50 mA g(-1), and a higher capacity of 4000 mA h g(-1) within 20 cycles at a rate as high as 200 mA g(-1). Moreover, the cell with the np-RuO2/nr-MnO2 catalyst presented much lower voltage polarization (about 0.58 V at a rate of 50 mA g(-1)) than that measured with only MnO2 nanorods during charge/discharge processes. The catalytic property of the np-RuO2/nr-MnO2 and MnO2 nanorods were further compared by conducting studies of using rotating disk electrode (RDE), chronoamperommetry and linear sweep voltammetry. The results illustrated that the np-RuO2/nr-MnO2 exhibited excellent bifunctional electrocatalytic activities towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, in-situ high-energy X-ray diffraction was employed to trace evolution of species on the np-RuO2/nr-MnO2 cathode during the discharge processes. In-situ XRD patterns demonstrated the formation process of the discharge products that consisted of mainly Li2O2. Ex-situ SEM images were recorded to investigate the morphology and decomposition of the sphere-like Li2O2, which could be observed clearly after discharge process, while are decomposed almost after charge process. The excellent electrochemical performances of the np-RuO2/nr-MnO2 as cathode of Li-O-2 battery could be contributed to the excellent bifunctional electrocatalytic activities for both the ORR and OER, and to the one-dimensional structure which would benefit the diffusion of oxygen and the storage of Li2O2 in the discharge process of Li-O-2 battery.

Xu, Yue-Feng↗

Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems

Lead sulfide (PbS) quantum dots (QDs) have shown promising performance as a sensitizer in infrared-to-visible photon upconversion systems. To investigate the key design rules, we compare three PbS-sensitized upconversion systems using three mediator molecules with the same tetracene triplet acceptor at different distances from the QD. Using transient absorption spectroscopy, we directly measure the triplet energy-transfer rates and efficiencies from the QD to the mediator and from the mediator to the emitter. With increasing distance between the mediator and PbS QD, the efficiency of the first triplet energy transfer from the QD to the mediator decreases because of a decrease in the rate of this triplet energy-transfer step, while the efficiency of the second triplet energy transfer from the mediator to the emitter increases because of a reduction in the QD-induced mediator triplet state decay. The latter effect is a result of the slow rate constant of the second triplet energy-transfer process, which is 3 orders of magnitude slower than the diffusion-limited value. The combined results lead to a net decrease of the steady-state upconversion quantum yield with distance, which could be predicted by our kinetic model. Our result shows that the QD/mediator interface affects both the first and second triplet energy transfer processes in the photon upconversion system, and the QD/mediator distance has an opposite effect on the efficiencies of the first and second triplet energy transfer. Lastly, these findings provide important insight for the further rational improvement of the overall efficiency of QD-based upconversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NINE-YEAR WILKINSON MICROWAVE ANISOTROPY PROBE (WMAP) OBSERVATIONS: FINAL MAPS AND RESULTS

We present the final nine-year maps and basic results from the Wilkinson Microwave Anisotropy Probe (WMAP) mission. The full nine-year analysis of the time-ordered data provides updated characterizations and calibrations of the experiment. We also provide new nine-year full sky temperature maps that were processed to reduce the asymmetry of the effective beams. Temperature and polarization sky maps are examined to separate cosmic microwave background (CMB) anisotropy from foreground emission, and both types of signals are analyzed in detail. We provide new point source catalogs as well as new diffuse and point source foreground masks. An updated template-removal process is used for cosmological analysis; new foreground fits are performed, and new foreground-reduced CMB maps are presented. We now implement an optimal C {sup –1} weighting to compute the temperature angular power spectrum. The WMAP mission has resulted in a highly constrained ΛCDM cosmological model with precise and accurate parameters in agreement with a host of other cosmological measurements. When WMAP data are combined with finer scale CMB, baryon acoustic oscillation, and Hubble constant measurements, we find that big bang nucleosynthesis is well supported and there is no compelling evidence for a non-standard number of neutrino species (N {sub eff} = 3.84 ± 0.40). The model fit also implies that the age of the universe is t {sub 0} = 13.772 ± 0.059 Gyr, and the fit Hubble constant is H {sub 0} = 69.32 ± 0.80 km s{sup –1} Mpc{sup –1}. Inflation is also supported: the fluctuations are adiabatic, with Gaussian random phases; the detection of a deviation of the scalar spectral index from unity, reported earlier by the WMAP team, now has high statistical significance (n{sub s} = 0.9608 ± 0.0080); and the universe is close to flat/Euclidean (Ω{sub k} = -0.0027{sup +0.0039}{sub -0.0038}). Overall, the WMAP mission has resulted in a reduction of the cosmological parameter volume by a factor of 68,000 for the standard six-parameter ΛCDM model, based on CMB data alone. For a model including tensors, the allowed seven-parameter volume has been reduced by a factor 117,000. Other cosmological observations are in accord with the CMB predictions, and the combined data reduces the cosmological parameter volume even further. With no significant anomalies and an adequate goodness of fit, the inflationary flat ΛCDM model and its precise and accurate parameters rooted in WMAP data stands as the standard model of cosmology.

79 ASTRONOMY AND ASTROPHYSICS↗

Near room-temperature direct encapsulation of organic photovoltaics by plasma-based deposition techniques

Plasma-assisted atomic layer deposition (ALD) is used for the deposition of environmental barriers directly onto organic photovoltaic devices (OPVs) at near room temperature (30 °C). To study the effect of the ALD process on the organic materials forming the device, the precursor diffusion and intermixing at the interface during the growth of different plasma-assisted ALD inorganic barriers (i.e. Al 2 O 3 and TiO 2 ) onto the organic photoactive layer (P3HT:ICBA) was investigated in this paper. Depth profile x-ray photoelectron spectroscopy was used to analyze the composition of the organic/inorganic interface to investigate the infiltration of the plasma-assisted ALD precursors into the photoactive layer as a function of the precursor dimension, the process temperature, and organic layer morphology. The free volume in the photoactive layer accessible to the ALD precursor was characterized by means of ellipsometric porosimetry (EP) and spectroscopic ellipsometry as a function of temperature. The organic layer is shown to exhibit free volume broadening at high temperatures, increasing the infiltration depth of the ALD precursor into the photoactive layer. Furthermore, based on previous investigations, the intrinsic permeation properties of the inorganic layers deposited by plasma-assisted ALD were predicted from the nano-porosity content as measured by EP and found to be in the 10 -6 gm -2 d -1 range. Insight from our studies was used to design and fabricate multilayer barriers synthesized at near-room temperature by plasma-assisted ALD in combination with plasma-enhanced CVD onto organic photovoltaic (OPVs) devices. Finally, encapsulated OPVs displayed shelf-lifetimes up to 1400 h at ambient conditions.

14 SOLAR ENERGY↗

Lattice Monte Carlo simulation of Galilei variant anomalous diffusion

The observation of an increasing number of anomalous diffusion phenomena motivates the study to reveal the actual reason for such stochastic processes. When it is difficult to get analytical solutions or necessary to track the trajectory of particles, lattice Monte Carlo (LMC) simulation has been shown to be particularly useful. To develop such an LMC simulation algorithm for the Galilei variant anomalous diffusion, we derive explicit solutions for the conditional and unconditional first passage time (FPT) distributions with double absorbing barriers. According to the theory of random walks on lattices and the FPT distributions, we propose an LMC simulation algorithm and prove that such LMC simulation can reproduce both the mean and the mean square displacement exactly in the long-time limit. However, the error introduced in the second moment of the displacement diverges according to a power law as the simulation time progresses. We give an explicit criterion for choosing a small enough lattice step to limit the error within the specified tolerance. We further validate the LMC simulation algorithm and confirm the theoretical error analysis through numerical simulations. The numerical results agree with our theoretical predictions very well.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

CO 2 capture properties of lithium silicates with different ratios of Li 2 O/SiO 2 : an ab initio thermodynamic and experimental approach

The lithium silicates have attracted scientific interest due to their potential use as high-temperature sorbents for CO 2 capture. The electronic properties and thermodynamic stabilities of lithium silicates with different Li 2 O/SiO 2 ratios (Li 2 O, i 8 SiO 6 , Li 4 SiO 4 , Li 6 Si 2 O 7 , Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 2 Si 3 O 7 , and a-SiO 2 ) have been investigated by combining first-principles density functional theory with lattice phonon dynamics. All these lithium silicates examined are insulators with band-gaps larger than 4.5 eV. By decreasing the Li 2 O/SiO 2 ratio, the first valence bandwidth of the corresponding lithium silicate increases. Additionally, by decreasing the Li 2 O/SiO 2 ratio, the vibrational frequencies of the corresponding lithium silicates shift to higher frequencies. Based on the calculated energetic information, their CO 2 absorption capabilities were extensively analyzed through thermodynamic investigations on these absorption reactions. We found that by increasing the Li 2 O/SiO 2 ratio when going from Li 2 Si 3 O 7 to Li 8 SiO 6 , the corresponding lithium silicates have higher CO 2 capture capacity, higher turnover temperatures and heats of reaction, and require higher energy inputs for regeneration. Based on our experimentally measured isotherms of the CO 2 chemisorption by lithium silicates, we found that the CO 2 capture reactions are two-stage processes: (1) a superficial reaction to form the external shell composed of Li 2 CO 3 and a metal oxide or lithium silicate secondary phase and (2) lithium diffusion from bulk to the surface with a simultaneous diffusion of CO 2 into the shell to continue the CO 2 chemisorption process. The second stage is the rate determining step for the capture process. By changing the mixing ratio of Li 2 O and SiO 2 , we can obtain different lithium silicate solids which exhibit different thermodynamic behaviors. Based on our results, three mixing scenarios are discussed to provide general guidelines for designing new CO2 sorbents to fit practical needs.

54 ENVIRONMENTAL SCIENCES↗

Solid-State Sintering of Core-Shell Ceramic Powders Fabricated by Particle Atomic Layer Deposition

The properties of technical ceramics are highly dependent on their microstructure, which evolves during sintering. Sintering is the process by which ceramic parts are subjected to high temperatures to activate chemical diffusion and the consumption of porosity. During the initial stage of sintering, interparticle necks between neighboring particles form and subsequently increase in size, consuming porosity as the particle centers move closer together. To experimentally determine how this process depends on particle surface composition, particle atomic layer deposition (ALD) was used to deposit a thin film of amorphous aluminum oxide (Al2O3) onto yttria-stabilized tetragonal zirconia (3YSZ) particles, producing core-shell structured powders. The uniformity of the Al2O3 film was confirmed with transmission electron microscopy and energy dispersive spectroscopy. Scanning electron microscopy was used to observe microstructural evolution during sintering, and the dihedral angles of Al2O3 and 3YSZ grains were measured to determine the ratio of interfacial energies between the 3YSZ|3YSZ, 3YSZ|Al2O3, and Al2O3|Al2O3 interfaces. Analysis of the densification kinetics revealed that the initial stage of densification is dependent on the material at the surface of the particles (ie, the Al2O3 film) and is controlled by the diffusion of Al3+ cations through Al2O3. Once the Al2O3 film has coalesced, the sintering behavior is controlled by the densification of the core material (3YSZ). Thus, core-shell powders fabricated by particle ALD sinter by a two-step process where the kinetics are dependent on the material present at interparticle contacts.

alumina↗