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At least 991 records · Page 55

Piezo-/dielectric properties of perovskite-structure high-temperature relaxor ferroelectrics: The Pb(Lu{sub 1/2}Nb{sub 1/2})O{sub 3}–Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3} ternary ceramics

Graphical abstract: - Highlights: • Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}-based ternary ferroelectric ceramics were prepared by solid-state synthesis method. • Morphotropic phase boundary region has been determined by XRD, di-/piezoelectric properties. • The compositions near MPB region exhibit excellent piezoelectric properties. - Abstract: A new compositional system of relaxor ferroelectrics was investigated based on the high piezoelectricity Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3} ferroelectric perovskite family. Compositions were fabricated near an estimated morphotropic phase boundary (MPB) of the Pb(Lu{sub 1/2}Nb{sub 1/2})O{sub 3}–Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}–PbTiO{sub 3} (PLZNT) ternary system by a two-step synthetic process. Their structures have been analyzed by means of X-ray diffraction technique. On the basis of X-ray powder diffraction, the morphotropic phase boundary (MPB) region for the ternary system was obtained. The Curie temperature T{sub C} of ternary system varied from 240 °C to 330 °C and the coercive fields E{sub c}s > 10 kV/cm. The values of piezoelectric coefficients d{sub 33} vary in the range of 260–450 pC/N with different PZN contents. It is worth noting that the optimum compositions were located at MPB region but near the tetragonal phase. The new PLZNT ceramics exhibit wider range of T{sub C}s and E{sub c}s, making it a promising material for high-powder ultrasound transducers using in a large temperature range.

36 MATERIALS SCIENCE↗

Improving the Strength of the ZrC-SiC and TC4 Brazed Joint Through Fabricating Graded Double-Layered Composite Structure on TC4 Surface

In order to improve the ZrC-SiC ceramic and TC4 brazed joint property, graded double-layered SiC particles (SiCp)-reinforced TC4-based composite structure (named as GLS for convenience) was designed to relieve the residual stress in the joint. The GLS was successfully fabricated on TC4 substrate by double-layered laser deposition technology before the brazing process. The investigation of the GLS shows that the volume fraction of SiCp in the two composite layers was graded (20 and 39 vol pct, respectively). Ti{sub 5}Si{sub 3} and TiC phases formed in the GLS due to the reaction of SiCp and TC4. The laser power-II (the laser power for the second deposition layer) affected the microstructure of the GLS significantly. Increasing the laser power-II would promote the reaction between the SiCp and TC4. But the high laser power-II made the layer I remelt completely and the two layers became homogeneous rather than graded structure. In the ZrC-SiC and TC4 brazed joint, the CTE (coefficient of thermal expansion) was graded from the TC4 to the ZrC-SiC due to the GLS, and the strength of the joint with the GLS (91 MPa) was higher than that without the GLS (43 MPa).

36 MATERIALS SCIENCE↗

Experimental study of three-dimensional CO 2 -water drainage and fracture-matrix interactions in fractured porous media

Estimation of CO 2 storage capacity in fractured porous reservoirs requires a better understanding of the CO 2 -water flow fundamentals in fracture-matrix systems. There are few core-flood experiments on three-dimensional CO 2 -water drainage in a fracture-matrix system, yet none have examined the impacts of the capillary continuity of fractures and fracture-matrix interactions. In this study, twelve drainage experiments were conducted in four fracture-matrix columns, each comprising a vertical stack of a cylindrical rock core, a filter paper serving as an analogue to a horizontal fracture, and a ceramic plate. Here, the core sample was surrounded by open space at the top and circumferential sides to model fractures, allowing for 3-D CO 2 -water drainage in the rock core and displaced water draining across the horizontal fracture. X-ray computed tomography was conducted to visualize the dynamic invasion/drainage processes in four rock core samples showing contrasts in anisotropy, permeability, and heterogeneity. Experimental results show (1) the equilibrium CO 2 saturations in the rock matrix vary from 0.10 to 0.60 at controlled capillary pressures up to 200 kPa, (2) the CO 2 saturations in the matrix increase with water saturation in the horizontal fracture resulting in better capillary continuity for water to drain across the fracture, and (3) the fracture water saturation can be enhanced by the non-uniform fracture capillary pressure and countercurrent flow of CO 2 and water across the fracture-matrix interface. In the case of high fracture water saturation, matrix CO 2 saturation largely depends on matrix anisotropy and heterogeneity. The core-scale experimental results contribute to understand the fracture-matrix interactions and CO 2 storage efficiency in fractured porous media.

54 ENVIRONMENTAL SCIENCES↗

A general flame aerosol route to high-entropy nanoceramics

High-entropy ceramics are an emerging class of materials with fascinating characteristics. However, elemental immiscibility and crystal complexity limit the development of a general synthesis strategy, and common methods yield bulk materials. Here, we introduce a transformative non-equilibrium flame aerosol technique for synthesizing high-entropy nanoceramics. This scalable, one-step process enables the production of high-entropy oxide nanoceramics with an unprecedented diversity of crystal structures, including fluorite-phase materials that integrate up to 22 distinct cation elements. The method’s capacity for entropic stabilization and grain refinement significantly improves the thermal stability of these nanostructures. In a representative application, a Pt-(MgCoNiCuZn)O high-entropy single-atom catalyst showed superior activity and long-term stability, maintaining constant CO 2 conversion over 670 h and dramatically outperforming conventional catalysts. Finally, the general approach opens a vast composition and structure space for the creation of high-entropy oxide nanomaterials for application across diverse fields, including catalysis, energy storage, sensing, and thermal management.

36 MATERIALS SCIENCE↗

Electrolyte Oxidation Pathways in Lithium-Ion Batteries

The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO 2 /Li cells were cycled with a lithium-ion conducting glass–ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ~4.7 V vs Li/Li + for LiCoO 2 ), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterized, and a detailed reaction scheme is constructed to rationalize the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have a direct impact on understanding and mitigating degradation in high-voltage/higher-energy-density LiCoO 2 -based cells, and more generally for cells containing nickel-containing cathode materials (e.g., LiNi x Mn y Co z O 2 ; NMCs), as they lose oxygen at lower operating voltages.

25 ENERGY STORAGE↗

Sintering protonic zirconate cells with enhanced electrolysis stability and Faradaic efficiency

The emerging applications of steam electrolysis and electrochemical synthesis at 300–600 °C set stringent requirements on the stability of protonic ceramic cells, which cannot be met by Ce-rich electrolytes. A promising candidate is Ce-free BaZr 0.8 Y 0.2 O 3–δ , but its usage has long been hindered due to the high sintering temperatures required for protonic devices. Here we resolved the issue through a co-sintering process, in which the shrinkage stress of a readily sinterable support layer helps to densify the pure BaZr 0.8 Y 0.2 O 3–δ electrolyte membrane at low temperatures. This approach eliminates Ce and harmful sintering aids in the dense zirconate electrolyte membrane, thereby enhancing the Faradaic efficiency and electrochemical stability, especially under harsh operating conditions. Here, the protonic zirconate cells have exceptional performance and demonstrate stable high-steam pressure electrolysis up to 0.7 atm steam pressure, –2 A cm –2 current density and over 800 h of dynamic operation at 600 °C. Our processing breakthrough enables stabilized protonic cells for demanding applications in future energy infrastructure.

25 ENERGY STORAGE↗

Dielectric and magnetic properties of some gadolinium silica nanoceramics

Some nanostructure gadolinium silica glass-ceramics were obtained undergoing a sol gel method and a heat-treatment at 1000°C about two hours. The magnetic and dielectric properties of these samples were studied. The magnetic properties were evidenced performing susceptibility measurements in the 80-300K temperature range. A Curie-Weiss behavior has acquired. The values estimated for paramagnetic Curie temperature being small and positive suggest the presence of weak ferromagnetic interactions between Gd{sup 3+} ions. The dielectric properties were evaluated from dielectric permittivity (ε{sub r}) and dielectric loss (tanδ) measurements at the frequency 1 kHz, 10 kHz and 100 kHz, in the 25-225°C temperature range and dielectric dispersion at room temperature for 79.5 kHz - 1GHz frequency area. The dielectric properties suggest that the main polarization mechanism corresponds to interfacial polarization, characteristic for polycrystalline-structured dielectrics. The polycrystalline structure of the samples is due to the polymorphous transformations of the nanostructure silica crystallites in the presence of gadolinium oxide. They were highlighted by SEM micrographs.

36 MATERIALS SCIENCE↗

Structural, ferroelectric and magnetic study of lead free (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}La{sub x}Ti{sub 0.988}Fe{sub 0.012}O{sub 3} (x=0,0.01,0.03,0.05) ceramic

Lead free (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}La{sub x}Ti{sub 0.988}Fe{sub 0.012}O{sub 3} ceramic having compositions (x=0, 0.01, 0.03, 0.05) has been prepared by sol gel method using citric acid. Structural analysis has been done by X-ray diffraction and FTIR measurements. XRD patterns have been confirmed perovskite structure for all samples. FTIR absorption band at around ∼630 cm{sup −1} is observed for all samples which confirm perovskite phase formation in samples. With increasing La concentration, shifting in XRD peaks and FTIR absorption bands is observed which suggests incorporation of La on A-site in prepared (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}La{sub x}Ti{sub 0.988}Fe{sub 0.012}O{sub 3} samples. Effect of La substitution on Ferroelectric (Polarization vs. Electric field) and Magnetic (Magnetization vs. Magnetic field) properties have been studied at room temperature. All samples exhibit weak ferromagnetic order and also possess ferroelectric behavior which provides new insight to lead free single phase multiferroic materials.

36 MATERIALS SCIENCE↗

Laboratory Optimization Tests of Technetium Decontamination of Hanford Waste Treatment Plant Direct Feed Low Activity Waste Melter Off-Gas Condensate Simulant

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream (LAW Off-Gas Condensate) from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable less integrated operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of glass waste.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sierra Space Technology Collaboration-Advanced Manufacturing of Thermal Protection System Tiles for Space Plane Atmospheric Reentry

Thermal protection systems (TPS) constitute a major material, engineering, and manufacturing challenge for space access. Atmospheric re-entry generates very high heats and requires advanced materials to withstand such conditions. Combining the required materials and integrating them into the vehicle is a major engineering undertaking that often must use creative designs to accommodate the selected materials and systems. Likewise, the manufacture of TPS is costly and challenging; it requires a combination of materials in a range of complex and unique shapes with specialized process conditions. Compounding these challenges, for harsh re-entry profiles or on high heat flux regions of the vehicle, even state of the art TPS is effectively single use and thereby creating a strong economic incentive to improve the TPS materials, integration, and manufacture. This work focuses on the use of ceramic modifications to TPS materials thereby allowing multi flight capability.

99 GENERAL AND MISCELLANEOUS↗

Advanced Manufacturing of Thermal Protection System Tiles for Space Plane Atmospheric Reentry

Thermal protection systems (TPS) constitute a major material, engineering, and manufacturing challenge for space access. Atmospheric re-entry generates very high heats and requires advanced materials to withstand such conditions. Combining the required materials and integrating them into the vehicle is a major engineering undertaking that often must use creative designs to accommodate the selected materials and systems. Likewise, the manufacture of TPS is costly and challenging; it requires a combination of materials in a range of complex and unique shapes with specialized process conditions. Compounding these challenges, for harsh re-entry profiles or on high heat flux regions of the vehicle, even state of the art TPS is effectively single use and thereby creating a strong economic incentive to improve the TPS materials, integration, and manufacture. This work focuses on the use of ceramic modifications to TPS materials thereby allowing multi flight capability.

36 MATERIALS SCIENCE↗

Microstructural and infiltration properties of woven preforms during chemical vapor infiltration

Interface-resolved direct numerical simulations (DNSs) of chemical vapor infiltration (CVI) have been performed over a range of furnace-operating conditions (Thiele moduli) and for practical woven preform geometries. A level-set method is used to resolve the geometry of the initial preform at tow scale. The interface between the vapor and solid phase is then evolved in time through the entire CVI densification cycle, fully resolving the time-varying topology between the two phases. In contrast to previous level-set methods for CVI simulation, the physical reaction and diffusion processes govern the level-set movement in the current approach. The surface deposition kinetics is described by the usual one-step model. In this paper, the DNS data are used to study the evolving porosity, surface-to-volume ratio, and flow infiltration properties (permeability and effective diffusivities). Additionally, comparisons are made to popularly-assumed structure functions and the standard, Kozeny–Carmen porous media model commonly employed in modeled CFD simulations of CVI. The virtual DNS experiments reveal a Thiele modulus and preform geometry (fabric layup) dependence which the existing microstructural and infiltration models are not able to describe throughout the entire densification process. The DNS-based, woven geometry-specific correlations can be applied directly to mean-field, furnace-scale CFD simulations.

36 MATERIALS SCIENCE↗

Microstructural, Optical, and Magnetic Properties of Vanadium-Substituted Nickel Spinel Nanoferrites

The current study investigates the impact of vanadium substitution on the structural, magnetic, and optical properties of NiFe{sub 2−x}V{sub x}O{sub 4} (x ≤ 0.3) nanoparticles (NPs) produced by the cost-effective sol-gel route. The as-prepared spinel ceramic powders were examined by X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (DRS), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). The functional groups, spinel phase, and crystal structure were confirmed by XRD and FT-IR, respectively. The crystallites size decreased from 45.24 to 36.56 nm as the doping process increases. The plots of Tauc were drawn to determine optical band gap magnitudes of 1.291, 1.302, and 1.312 eV for x = 0.0, 0.2, and 0.3, respectively. The estimated saturation magnetization is maximum for pristine NiFe{sub 2}O{sub 4} NPs and decreases to minimum for NiFe{sub 1.7}V{sub 0.3}O{sub 4} NPs. The σ-H hysteresis loops have finite coercivity (between 125 and 169 Oe) and retentivity (between 9.36 and 14.04 emu/g) values. The calculated σ{sub r}/σ{sub s} ratios are lower than 0.500, assigning the uniaxial anisotropy for NiFe{sub 2−x}V{sub x}O{sub 4}. The effective anisotropy constants (K{sub eff}) are in the range of 0.824 × 10{sup 5} and 1.303 × 10{sup 5} Erg/g. The magnetocrystalline anisotropy field (H{sub a}) values are around 5.0 kOe. The characteristics of hysteresis (σ-H) curves and the order of magnetic data reveal the soft ferrimagnetic feature of as-prepared nanoparticle samples. From Mossbauer analysis, the variations in hyperfine magnetic field, quadrupole splitting, line width, and isomer shift have been evaluated. The distribution of cations showed that the octahedral B sites are occupied by all the ions of V{sup 3+}. Mossbauer spectra are composed of four Zeeman sextets and one doublet.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

An air-stable Na 3 SbS 4 superionic conductor prepared by a rapid and economic synthetic procedure

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3 SbS 4 , a novel Na superionic conductor that needs much lower processing temperature below 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.

25 ENERGY STORAGE↗

Carbon Molecular Sieve Membrane Preparation by Economical Coating and Pyrolysis of Porous Polymer Hollow Fibers

Dip coating and pyrolysis processes are needed to create multi-layer asymmetric carbon molecular sieve (CMS) hollow fiber membranes with excellent gas separation properties. Coating of an economical engineered support with a high-performance polyimide to create precursor fibers with a dense skin layer reduces material cost by 25-fold compared to monolithic precursors or ceramic supports. CMS permeation results with CO 2 /CH 4 (50:50) mixed gas feed reflect attractive CO 2 /CH 4 selectivity of 58.8 and CO 2 permeance of 310 GPU at 35 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state rigid-rod polymer composite electrolytes with nanocrystalline lithium ion pathways

A critical challenge for next-generation lithium-based batteries lies in development of electrolytes that enable thermal safety along with use of high-energy-density electrodes. We describe molecular ionic composite (MIC) electrolytes based on an aligned liquid crystalline polymer combined with ionic liquids and concentrated Li salt. This high strength (200 MPa) and non-flammable solid electrolyte possesses outstanding Li + conductivity (1 mS cm -1 at 25 °C) and electrochemical stability (5.6 V vs Li|Li + ) while suppressing dendrite growth and exhibiting low interfacial resistance (32 Ω cm 2 ) and overpotentials (≤ 120 mV @ 1 mA cm -2 ) during Li symmetric cell cycling. A heterogeneous salt doping process modifies a locally ordered polymer-ion assembly to incorporate an inter-grain network filled with defective LiFSI & LiBF 4 nanocrystals, strongly enhancing Li + conduction. Furthermore, this modular material fabrication platform shows promise for safe and high-energy-density energy storage and conversion applications, incorporating the fast transport of ceramic-like conductors with the superior flexibility of polymer electrolytes.

25 ENERGY STORAGE↗