Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “DENSIFICATION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Micro-tensile characteristics of As-fabricated and irradiated AGR-2 TRISO fuel particle buffer, IPyC, and buffer-IPyC interlayer regions

A recently developed micro-tensile sample preparation technique was implemented to evaluate the tensile strengths of the buffer, IPyC, and buffer-IPyC interlayer regions of the unirradiated and irradiated AGR-2 TRISO fuel particles. Understanding the mechanical properties of the buffer-IPyC interlayer is essential for developing thermomechanical models of buffer-IPyC separation, yet there is a lack of experimental data on its micro-tensile properties. TEM analysis was conducted on these regions to determine the microstructural changes relevant to the samples' tensile properties. In the unirradiated TRISO particle samples, the buffer layer demonstrated the weakest tensile strength, while the IPyC layer exhibited the highest. Conversely, in the irradiated TRISO particle samples, the buffer-IPyC interlayer region showed the lowest tensile strength, with the IPyC layer being the strongest. Fractures in the samples from the buffer-IPyC region predominantly occurred either in the buffer layer or at the buffer-IPyC interface. However, some buffer-IPyC interlayer samples displayed stress-strain and fracture behaviors more akin to the IPyC layer than the buffer layer. Analysis of diffraction patterns suggests that irradiation may have increased anisotropy in the three regions tested. Despite this suggested increase in anisotropy, there was no evidence that it affected the measured strengths. The irradiated TRISO particles demonstrated a considerable increase in void space and a decrease in ultimate tensile strength within the buffer-IPyC interlayer region due to the densification and contraction of the buffer layer. Minor variations in diffraction ring patterns were also observed. These changes, coupled with a significant reduction in the Weibull modulus/shape parameter, imply that irradiation-induced densification leads to tearing between the buffer and IPyC layers at locations of elevated porosity in the buffer-IPyC interlayer region.

Tristructural isotropic (TRISO)↗
DOE OSTI2026

The influence of iron incorporation on the microstructure and crystal chemistry of UO 2 fuel

The incorporation of dopants into UO 2 is of interest for both doped advanced fuel and nuclear forensics research. Suitable forensics dopants, or taggants, for nuclear fuels are ones that do not adversely affect the performance of the parent material while still being traceable during key stages of the fuel’s life cycle. In this paper, we present our efforts to understand the effects of doping UO 2 with Fe 2 O 3 under multiple parameters, such as Fe concentration (0–3000 wppm), sintering temperature (1673 K, 1773 K, and 1973 K), sintering time (2–12 h), and atmosphere (reducing and inert). Here, we investigated densification behavior, microstructure evolution, and lattice defects based on the geometric densities, scanning electron microscopy (SEM), X-ray diffractograms, and Raman spectra. The effect of Fe on the microstructure and crystal chemistry of UO 2 is very complex, especially at the intermediate temperature (1773 K), where we found that densification kinetics are enhanced and that lattice contraction occurs for doping concentrations greater than 1000 wppm Fe.

Crystallography↗
DOE OSTI2025

Effect of high scandium doping in barium zirconate on nickel diffusion and performance of proton-conducting solid oxide electrolyzer cells

Proton-conducting solid oxide electrolyzer cells (p-SOECs) are emerging but promising technologies for hydrogen production. However, due to the lack of a robust electrolyte, p-SOECs struggle simultaneously to display high performance, Faradaic efficiency, and durability. Motivated by its high proton concentrations and stability as a barium zirconate, we have investigated BaZr 0.6 Sc 0.4 O 3-δ (BZSc40) as a potential next-generation p-SOEC electrolyte. Here, we found elevated levels of NiO diffusion through BZSc40 electrolytes during high-temperature sintering, attributed to the large oxygen vacancy concentrations present in BZSc40, as revealed by first-principle computational results. Controlling NiO diffusion is critical, as it can facilitate densification and grain size growth, but it may also detrimentally impact performance by causing electronic leakage. By optimizing sintering temperature when fabricating BZSc40 cells, we successfully controlled NiO diffusion, achieving sufficient electrolyte densification along with high performance and Faradaic efficiency. BZSc40 cells reached −0.99 A/cm 2 at 1.3 V and 600 °C and exhibited enhanced durability with a 3.37 mV/kh degradation rate at −0.8 A/cm 2 over a 200-h testing period. BZSc40 electrolytes demonstrated superior performance over BaZr 0.8 Y 0.2 O 3-δ (BZY20). In addition to elevated current densities and grain sizes, BZSc40 cells achieved Faradaic efficiencies of 76 % compared to 54 % for BZY20 at −0.2 A/cm 2 and 600 °C. This work lays the foundation for BZSc40 as a potential electrolyte due to its advantages over BZY20 while demonstrating the significance of controlling NiO diffusion when fabricating p-SOECs.

Electrolyzer↗
DOE OSTI2012

Effect of phosphorus additions on the sintering and transport properties of proton conducting BaZr{sub 0.85}Y{sub 0.15}O{sub 3-{delta}}

The influence of phosphorous additions on the sintering and electrical transport properties of the proton-conducting perovskite BaZr{sub 0.85}Y{sub 0.15}O{sub 3-{delta}} (BZY) has been studied with a view to the use of phosphates as typical dispersants for the formation of stabilised solid suspensions or as possible sintering aids. P{sub 2}O{sub 5} additions, (1-x)BZY{center_dot}xP{sub 2}O{sub 5}, monotonously promote densification in the intermediate compositional range 0.04{<=}x{<=}0.08. Nonetheless, BZY reacts with phosphorous forming the phase Ba{sub 3}(PO{sub 4}){sub 2} at temperatures as low as 600 Degree-Sign C. The associated loss of Ba from the perovskite, leads to a decrease in the perovskite lattice parameter, the formation of yttria-based impurity phases and impaired grain growth. Such reaction has an extremely detrimental effect on bulk and grain boundary conductivities. It is, therefore, vital that the current results are taken into account by the protonics community when attempting to prepare the stabilised solid suspensions of BZY nanopowders required for thin ceramic applications. Alternative dispersants to phosphate esters must be found. - Graphical Abstract: Sintering experiments performed at 1500 Degree-Sign C for 5 h and at 1400 Degree-Sign C for 24 h of (1-x)BaZr{sub 0.85}Y{sub 0.15}O{sub 3-{delta}}{center_dot}xP{sub 2}O{sub 5} in the range x=0-0.10. Highlights: Black-Right-Pointing-Pointer P{sub 2}O{sub 5} additions, (1-x)BZY{center_dot}xP{sub 2}O{sub 5}, promote densification in the intermediate compositional range 0.04{<=}x{<=}0.08. Black-Right-Pointing-Pointer BZY reacts with phosphorous forming the phase Ba{sub 3}(PO{sub 4}){sub 2} at temperatures as low as 600 Degree-Sign C. Black-Right-Pointing-Pointer Detrimental effects on bulk and grain boundary conductivities are shown. Black-Right-Pointing-Pointer Alternative dispersants to phosphate esters must be found.

36 MATERIALS SCIENCE↗
DOE OSTI2015

High-pressure densified solid solutions of alkaline earth hexaborides (Ca/Sr, Ca/Ba, Sr/Ba) and their high-temperature thermoelectric properties

Solid solutions of alkaline earth hexaborides were synthesized and densified by spark plasma sintering at 100 MPa. The high-temperature thermoelectric properties (Seebeck coefficients, electrical and thermal diffusivities, heat capacities) were measured between room temperature and 1073 K. CaB{sub 6}, SrB{sub 6}, BaB{sub 6} and the ternary hexaborides Ca{sub x}Sr{sub 1−x}B{sub 6}, Ca{sub x}Ba{sub 1−x}B{sub 6}, Sr{sub x}Ba{sub 1−x}B{sub 6} (x = 0.25, 0.5, 0.75) are n-type conducting compounds over the whole compositional and thermal ranges. The values of the figure of merit ZT for CaB{sub 6} (ca. 0.3 at 1073 K) were found to be significantly increased compared to earlier investigations which is attributed to the densification process. - Highlights: • Solid solutions of alkaline earth hexaborides were synthesized. • High-temperature thermoelectric properties of mixed calcium borides are excellent. • Spark plasma source densification results in high ZT values. • Borides are rare-earth free and refractory materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Bottom-up processing and low temperature transport properties of polycrystalline SnSe

A hydrothermal approach was employed to efficiently synthesize SnSe nanorods. The nanorods were consolidated into polycrystalline SnSe by spark plasma sintering for low temperature electrical and thermal properties characterization. The low temperature transport properties indicate semiconducting behavior with a typical dielectric temperature dependence of the thermal conductivity. The transport properties are discussed in light of the recent interest in this material for thermoelectric applications. The nanorod growth mechanism is also discussed in detail. - Graphical abstract: SnSe nanorods were synthesized by a simple hydrothermal method through a bottom-up approach. Micron sized flower-like crystals changed to nanorods with increasing hydrothermal temperature. Low temperature transport properties of polycrystalline SnSe, after SPS densification, were reported for the first time. This bottom-up synthetic approach can be used to produce phase-pure dense polycrystalline materials for thermoelectrics applications. - Highlights: • SnSe nanorods were synthesized by a simple and efficient hydrothermal approach. • The role of temperature, time and NaOH content was investigated. • SPS densification allowed for low temperature transport properties measurements. • Transport measurements indicate semiconducting behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Microstructure and mechanical properties of NiCoCrAlYTa alloy processed by press and sintering route

Nickel-based superalloys such as NiCoCrAlY are widely used in high-temperature applications, such as gas turbine components in the energy and aerospace industries, due to their strength, high elastic modulus, and high-temperature oxidation resistance. However, the processing of these alloys is complex and costly, and the alloys are currently used as a bond coat in thermal barrier coatings. In this work, the effect of cold press and sintering processing parameters on the microstructure and mechanical properties of NiCoCrAlY alloy were studied using the powder metallurgy route as a new way to obtain NiCoCrAlYTa samples from a gas atomized prealloyed powder feedstock. High mechanical strength and adequate densification up to 98% were achieved. The most suitable compaction pressure and sintering temperature were determined for NiCoCrAlYTa alloy through microstructure characterization. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy dispersive spectroscopy microanalysis (EDS) were performed to confirm the expected γ-Ni matrix and β-NiAl phase distribution. Additionally, the results demonstrated the unexpected presence of carbides and Ni–Y-rich zones in the microstructure due to the powder metallurgy processing parameters used. Thus, microhardness, nanoindentation and uniaxial compression tests were conducted to correlate the microstructure of the alloy samples with their mechanical properties under the different studied conditions. The results show that the compaction pressure did not significantly affect the mechanical properties of the alloy samples. In this work, the compaction pressures of 400, 700 and 1000 MPa were used. The sintering temperature of 1200 °C for NiCoCrAlYTa alloy was preferred; above this temperature, the improvement in mechanical properties is not significant due to grain coarsening, whereas a lower temperature produces a decrease in mechanical properties due to high porosity and poor solid-state diffusion. - Graphical abstract: Display Omitted - Highlights: • We made NiCoCrAlYTa alloy by a conventional powder metallurgy route. • High densification and adequate strength were observed. • The presence of unexpected carbides found along γ/γ and γ/β grain boundaries was detected. • The effect of cold press and sintering processing parameters on the microstructure and mechanical properties were studied.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Research on the interfacial structure and property improvement of the Cfiber/2Si-B-3C-N ceramic matrix composite

Highlights: • The C{sub fiber}/2Si-B-3C-N composite with nice properties was successfully prepared. • ZrO{sub 2} promotes the densification process, homogeneous nucleation and grain growth. • The interface reaction in the composite was well controlled by the addition of ZrO{sub 2}. • The damage to carbon fiber was largely avoided by the addition of ZrO{sub 2}. - Abstract: A mixture of the mechanically alloyed 2Si-B-3C-N powder and short carbon fiber was hot pressed at 1800 °C for 30 mins in nitrogen. Careful investigation to the prepared C{sub fiber}/2Si-B-3C-N ceramic matrix composite revealed that the composite was very difficult to be densified. Heterogeneous nucleation, abnormal grain growth and severe interface reaction occurred on the fiber surface or between the fiber and the ceramic matrix, leading to a small density and weak mechanical properties of the composite. For the prepared composite without any additive, the relative density, flexural strength, elastic modulus and fracture toughness is 71.7%, 64.6 MPa, 14.7 GPa and 1.47 MPa·m{sup 1/2}, respectively. The average size of the SiC grains close to and far away from the carbon fiber is 249.10 nm and 50.45 nm, respectively. However, with the addition of ZrO{sub 2} (7.5 mol%), the above mentioned phenomenons are changed noticeably, and those properties are significantly increased to 88.5%, 112.4 MPa, 111.1 GPa and 2.94 MPa·m{sup 1/2}, respectively. At the same time, the SiC grains close to or far away from the carbon fiber almost have the same average size of about 448.21 nm, and almost no interface reaction occurs. It shows that the addition of ZrO{sub 2} not only facilitates the sintering and densification process, but also depresses the interface reaction, promotes the homogeneous nucleation and grain growth, and hence significantly improves the mechanical properties of the C{sub fiber}/2Si-B-3C-N composite. This interesting finding is favorable for the preparation of carbon fiber reinforced ceramic matrix composite, which requires both a large relative density and well controlled interface reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Solidification pattern, microstructure and texture development in Laser Powder Bed Fusion (LPBF) of Al10SiMg alloy

Highlights: • The complex solidification pattern during Laser Powder Bed Fusion of Al10SiMg alloy is explained. • The evolution of α-Al cellular network, grain structure and texture development is characterized. • The grain structure is shown to be columnar throughout the printed sample • The grains’ orientation align with that of the α-Al cells. • The size evolution of α-Al cells and grains within the scan tracks follow opposite patterns. • Utilizing of a 67° hatch angle enhances densification and promotes a more isotropically developed texture across the build. - Abstract: A comprehensive analysis of solidification patterns and microstructural development is presented for an Al10SiMg sample produced by Laser Powder Bed Fusion (LPBF). Utilizing a novel scanning strategy that involves counter-clockwise rotation of the scan vector by 67° upon completion of each layer, a relatively randomized cusp-like pattern of protruding/overlapping scan tracks has been produced along the build direction. We show that such a distribution of scan tracks, as well as enhancing densification during LPBF, reduces the overall crystallographic texture in the sample, as opposed to those normally achieved by commonly-used bidirectional or island-based scanning regimes with 90° rotation. It is shown that, under directional solidification conditions present in LPBF, the grain structure is strictly columnar throughout the sample and that the grains' orientation aligns well with that of the α-Al cells. The size evolution of cells and grains within the melt pools, however, is shown to follow opposite patterns. The cells'/grains' size distribution and texture in the sample are explained via use of analytical models of cellular solidification as well as the overall heat flow direction and local solidification conditions in relation to the LPBF processing conditions. Such a knowledge of the mechanisms upon which microstructural features evolve throughout a complex solidification process is critical for process optimization and control of mechanical properties in LPBF.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Establishing a process-structure-property-performance framework for SLS additive manufacturing through integrated multiscale modeling

This study presents a comprehensive suite of high-fidelity computational models that integrate multiscale and multiphysics simulations to capture the full Selective Laser Sintering (SLS) additive manufacturing process—from initial melting and solidification to mechanical response under external loads. Process simulations are linked with mechanical analysis through Representative Volume Elements (RVEs), establishing a process-structure–property-performance framework. The interaction between laser light and polyamide 12 (PA12) powder is modeled, accounting for laser characteristics and the optical, thermal, and geometrical properties of the powder. The heat source is incorporated into a heat transfer model, coupled with crystallization kinetics and densification models to predict material density and crystallinity. The porosity distribution from the densification model and crystallinity interpolated from experimental data are used to construct the RVEs. A multi-mechanism constitutive model is then calibrated using mechanical tests to predict the stress–strain response. Simulation results show good agreement with experimental data in terms of porosity, crystallinity, and mechanical performance when sufficient laser power (62 W or higher) is used. This research supports the inverse design of 3D-printed structures by introducing a high-fidelity framework that combines multiscale and multiphysics modeling with experimental calibration for predictive and performance-driven additive manufacturing.

SLS↗
DOE OSTI2013

Phase transformation, thermal expansion and electrical conductivity of lanthanum chromite

Graphical abstract: - Highlights: • Orthorhombic and rhombohedral phases co-exist at ≥260 °C and cubic above 1000 °C. • Polymorphic changes with temperature in air and Ar–3%H{sub 2} are observed. • Lattice volume change in Ar–3%H{sub 2} atmosphere corresponds to Cr{sup 4+} → Cr{sup 3+} transition. • Change in valence state of Cr{sup 4+} to Cr{sup 3+} results in lower electrical conductivity. • Experimental evidence is provided for poor densification of LaCrO{sub 3} in air. - Abstract: This paper addresses discrepancies pertaining to structural, thermal and electrical properties of lanthanum chromite. Experimental evidence is provided to support the hypothesis for poor densification in air as well as reduction in electrical conductivity in reducing atmosphere. Sintering condition for the synthesis of LaCrO{sub 3} was optimized to 1450 °C and 10 h. Thermo-analytical (differential scanning calorimetry – DSC) and high temperature X-ray diffraction (HT-XRD) studies show that orthorhombic lanthanum chromite transforms into rhombohedral structure at ∼260 °C and cubic structure above 1000 °C. Co-existence of the structural phases and the variation in each polymorph with temperature in both air and 3%H{sub 2}–Ar atmosphere is reported. Presence and absence of Cr-rich phase at inter-particle neck are observed in oxidizing and reducing atmospheres respectively. The linear thermal expansion co-efficient was calculated to be 10.8 ± 0.2 × 10{sup −6} °C{sup −1} in the temperature range of RT–1400 °C. Electrical conductivity of lanthanum chromite was found to be 0.11 S/cm in air. A decrease in electrical conductivity (0.02 S/cm at 800 °C) of LaCrO{sub 3}, as observed in reducing atmosphere (3%H{sub 2}–Ar), corresponds to lattice volume change as indicated by peak shift in HT-XRD results.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Comparison Between Simulated And Experimental Au-ion Profiles Implanted in nanocrystalline ceria

Radiation response of nanocrystalline ceria films deposited on a silicon substrate was investigated under a 3-MeV Au-ion irradiation at 300 K. A uniform grain growth cross the ceria films is observed and effective densification of the ceria thin films occurs during irradiation. The Au ion profiling was measured by secondary ion mass spectrometry (SIMS) and compared to the Au ion distribution predicted by the Stopping and Range of Ions in Solids (SRIM) code. It is observed that the Au-ion penetration depth is underestimated in comparison with the SIMS measurements. An overestimation of the electronic stopping power for heavy incident ions in the SRIM program may account for the discrepancies between the calculations and the SIMS experimental results. This work presents an approach to compensate the overestimation of the electronic stopping powers in the SRIM program by adjusting the nanocrystalline ceria target density to better predict the ion implantation profile.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

Thermal Evolution of Internal Strain in Doped PbTe

Recent improvements in the efficiency of heat-to-electricity energy conversion in lead chalcogenide thermoelectrics involve reducing the thermal conductivity by incorporating large amounts of internal strain. The extent to which typical lead chalcogenide processing techniques (such as doping, ball milling, and densification) increase internal strain and dislocation density must be quantified to improve materials design. In this study, neutron powder diffraction is leveraged to evaluate the internal strain introduced by ball milling in doped and undoped powders. Doping with Na and/or Eu increases internal strain beyond ball milling alone, with the greatest increase from combining the two dopants. Strain recovery occurs in each powder above 400 K but can be suppressed by co-doping, indicating a strong dopant–dislocation interaction in this system. Therefore, high-temperature processing of PbTe powders should be avoided if high internal strain is desired. Low-temperature densification and/or rapid pressing techniques may be key to maintaining internal strain in the final pressed pellet. The diffraction peak asymmetry and correlated elastic softening measured in pressed PbTe pellets in past studies were not observed in the precursor powders measured here, suggesting that measurements of the Debye temperature on final pressed pellets are required to examine the influence of defect-induced elastic softening on thermal conductivity. This work provides key guidance for defect engineering to maximize internal strain and thermoelectric performance in PbTe thermoelectrics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ultrafast Sintering and Dopant Effects in Garnet LLZO Solid Electrolytes

High-throughput, low-cost manufacturing, and optimization of solid electrolytes are necessary for the adoption of solid-state batteries. In this work, garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) with different aliovalent dopants, 𝑇𝑎$_{^·_{𝑍𝑟}}$, 𝐴𝑙$^{··}_{𝐿𝑖}$, and 𝐺𝑎$^{··}_{𝐿𝑖}$, have been ultrafast-sintered with different temperature ramping rates. The densification behavior, phases, their evolution, and surface chemistry of different LLZO have been investigated and linked to their electrochemical performances. It has been shown that LLZO with 𝑇𝑎$_{^·_{𝑍𝑟}}$ dopant demonstrates the highest garnet phase purity and overall best electrochemical performances, and ultrafast sintering further improves densification, ionic conductivity, and electrochemical stability. On the other hand, LLZO doped with 𝐴𝑙$^{··}_{𝐿𝑖}$ and 𝐺𝑎$^{··}_{𝐿𝑖}$ are reaching higher cubic phase purities and ionic conductivities via conventional sintering, indicating undesirable dopant migration and segregation during the ultrafast sintering process. In conclusion, these findings provide insights into the manufacturing of solid electrolyte materials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Exploring Pore Formation of Atomic Layer-Deposited Overlayers by in Situ Small- and Wide-Angle X-ray Scattering

In this work, we explore the pore structure of overcoated materials by in situ synchrotron small- and wide-angle X-ray scattering (SAXS)/(WAXS). Thin films of aluminum oxide (Al2O3) and titanium dioxide (TiO2) with thicknesses of 4.9 and 2.5 nm, respectively, are prepared by atomic layer deposition (ALD) on non-porous nanoparticles. In situ X-ray measurements reveal that porosity is induced in the ALD films by annealing the samples at high temperature. Moreover, this pore formation can be attributed to densification resulting from an amorphous to crystalline phase transition of the ALD films as confirmed by high resolution X-ray diffraction (XRD) and pair distribution function (PDF). Simultaneous SAXS/WAXS results not only show that the porosity is formed by this phase transition but also that the pore size increases with temperature.

Li, Tao↗
DOE OSTI2018

Swelling and Diffusion during Methanol Sorption into Hydrated Nafion

Diffusion within polymer electrolyte membranes is often coincident with time-dependent processes such as swelling and polymer relaxation, which are factors that limit their ability to block molecular crossover during use. The solution-diffusion model of membrane permeation, which is the accepted theory for dense polymers, applies only to steady-state processes and does not address dynamic internal structural changes that can accompany permeation. To begin discovery of how such changes can be coupled to the permeation process, we have constructed here a stochastic multiscale reaction-diffusion model that examines time-dependent methanol uptake into and swelling of hydrated Nafion. Several potential mechanisms of diffusion and polymer response are tested. The simulation predictions are compared to real-time Fourier transform infrared attenuated total reflectance spectroscopy (FTIR-ATR) absorbance reported in the literature [ Hallinan , D. T. , Jr. ; Elabd , Y. A. J. Phys. Chem. B 2007 , 111 , 13221 - 13230 ]. Of the proposed polymer response mechanisms, only one, a reaction-limited, local response to increasing methanol concentration that takes the entire experimental time frame of 600 s, produces simulated FTIR-ATR data consistent with experiment. The simulations show that water diffusion out of the membrane is minimal during methanol sorption and that changes in the measured infrared absorbances are due primarily to the increase in methanol concentration accompanied by dilution of water during swelling. Swelling involves densification of the polymer structure even as there is an overall volume expansion of the film. Potential connections between the polymer densification and molecular-level structural changes of Nafion in methanol are discussed. These results indicate that the interaction between methanol and Nafion serves to increase Nafion's capacity to accommodate large volumes of methanol-water solutions, facilitating increased permeation across the membrane relative to pure water.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Pressure-Driven Chemical Disorder in Glassy As 2 S 3 up to 14.7 GPa, Postdensification Effects, and Applications in Materials Design

A small difference in energy between homopolar and heteropolar bonds and the glass-forming ability of pure chalcogens leads to unexpected trends in densification mechanisms of glassy chalcogenides compared to vitreous oxides. Using high-precision compressibility measurements and in situ high-energy X-ray diffraction up to 14.7 GPa, we show herein a new densification route in a canonical glass As 2 S 3 . After the first reversible elastic step with a maximum pressure of 1.3 GPa, characterized by a strong reduction of voids and cavities, a significant bonding or chemical disorder is developed under higher pressure, reaching a saturation of 30% in the population of As-As bonds above 8-9 GPa. The pressure-driven chemical disorder is accompanied by a remarkable structural relaxation and a strongly diminished optical gap and determines structural, vibrational, and optical properties under and after cold compression. The decompressed recovered glass conserves a dark color and exhibits two relaxation processes: (a) fast (a few days) and (b) slow (months/years at room temperature). The enhanced refractive index of the recovered glass is promising for optical applications with improved functionalities. A nearly permanent red shift in optical absorption after decompression can be used in high-impact-force optical sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗