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At least 379 records · Page 21

3D Printed Optical Quality Silica and Silica-Titania Glasses from Sol-Gel Feedstocks

We report a method for fabricating optical quality silica and silica-titania glasses by additive manufacturing, or 3D printing. Key to this success was the combination of sol-gel derived silica and silica-titania colloidal feedstocks, 3D direct ink writing (DIW) technology, and conventional glass thermal processing methods. Printable silica and silica-titania sol inks were prepared directly from molecular precursors by a simple one-pot method, which was optimized to yield viscous, shear-thinning colloidal suspensions with tuned rheology ideal for DIW. After printing, the parts were dried and sintered under optimized thermal conditions to ensure complete organic removal and uniform densification without crystallization. Characterizations of the 3Dprinted pure silica and silica-titania glasses show that they are equivalent to commercial optical fused silica (Corning® 7980) and silica-titania glasses (Corning ULE® 7972). More specifically they exhibit comparable chemical composition, SiO2 network structure, refractive index, dispersion, optical transmission, and coefficient of thermal expansion. 3D printed silica and silica-titania glasses also exhibited comparable polished surface roughness and meet refractive index homogeneity standards within range of commercial optical grade glasses. This method establishes 3D printing as a viable tool to create optical glasses with compositional and geometric configurations that are inaccessible by conventional optical fabrication methods.

36 MATERIALS SCIENCE↗

Demonstration of the Reproducibility Challenges in the Sintering Behavior of Lithium‐Stuffed Garnets in Scaling up Synthesis

Lithium-stuffed garnets, such as Li 7 La 3 Zr 2 O 12 (LLZO), are promising candidates for next-generation solid-state batteries because of their high room-temperature ionic conductivity and chemical stability against lithium metal anodes, which are crucial for achieving higher energy density. However, realizing LLZO's potential in practical devices requires synthesis methods that can be scaled reliably to large batch sizes for manufacturing. Herein, we investigate the sintering reproducibility of LLZO synthesized at larger scales using ultrasonic spray pyrolysis, a cost-effective and scalable synthesis route. Two 100 g batches of Al-doped LLZO are prepared and their sintering behavior is examined in detail. Both Al-LLZO batches contain over 90 wt.% cubic-phase LLZO, and both batches exhibit room temperature conductivities greater than 1 × 10 −4 S cm −1 at a relative density above 0.8. However, variations in secondary phases and subtle differences in Al content lead to significant differences in densification and microstructure. These results demonstrate that LLZO's sintering behavior is highly sensitive to small changes in secondary phases and Al content, creating reproducibility challenges when moving from laboratory- to manufacturing-scale synthesis.

36 MATERIALS SCIENCE↗

Distinct Melt Infusion Architectures of Antiperovskite Solid Electrolytes

Antiperovskite solid electrolytes are an emerging class of lithium‐ion conductors distinguished by their unusually low melting points, enabling scalable, low‐temperature processing routes not accessible to most solid electrolytes. In this work, we synthesize phase‐pure chloride (Cl), bromide (Br), and mixed halide (ClBr) variants of antiperovskites and investigate their ionic conductivities in both powder and hot‐pressed forms. Hot pressing significantly enhances conductivity across all compositions, while energy‐dispersive X‐ray spectroscopy (EDS) of the mixed halide system reveals halide surface migration during densification. We further investigate the melt‐infiltration behavior of these electrolytes into substrates relevant to solid‐state battery architectures, including Al and Cu current collectors, conventional NMC and LFP cathodes, and a foamed NMC cathode with a highly porous architecture. The foamed cathode enables deep and uniform electrolyte penetration, highlighting the role of electrode architecture in facilitating melt infiltration. Across all substrates, electrolyte halide chemistry strongly influences wetting behavior, penetration depth, and resulting microstructural morphology. Together, these results establish clear processing–structure relationships for melt‐infiltrated antiperovskite solid electrolytes and demonstrate how electrolyte chemistry and electrode architecture govern interfacial morphology during integration, providing practical guidelines for processing and structural design in solid‐state battery systems.

antiperovskite↗

A spatially distributed model for assessment of the effects of changing land use and climate on urban stream quality: Development of a Spatially Distributed Urban Water Quality Model

While the effects of land use change in urban areas have been widely examined, the combined effects of climate and land use change on the quality of urban and urbanizing streams have received much less attention. We describe a modeling framework that is applicable to the evaluation of potential changes in urban water quality and associated hydrologic changes in response to ongoing climate and landscape alteration. The grid-based spatially distributed model, DHSVM-WQ, is an outgrowth of the Distributed Hydrology-Soil-Vegetation Model (DHSVM) that incorporates modules for assessing hydrology and water quality in urbanized watersheds at a high spatial and temporal resolution. DHSVM-WQ simulates surface runoff quality and in-stream processes that control the transport of nonpoint-source (NPS) pollutants into urban streams. We configure DHSVM-WQ for three partially urbanized catchments in the Puget Sound region to evaluate the water quality responses to current conditions and projected changes in climate and/or land use over the next century. Here we focus on total suspended solids (TSS) and total phosphorus (TP) from nonpoint sources (runoff), as well as stream temperature. The projection of future land use is characterized by a combination of densification in existing urban or partially urban areas, and expansion of the urban footprint. The climate change scenarios consist of individual and concurrent changes in temperature and precipitation. Future precipitation is projected to increase in winter and decrease in summer, while future temperature is projected to increase throughout the year. Our results show that urbanization has a much greater effect than climate change on both the magnitude and seasonal variability of streamflow, TSS and TP loads largely due to substantially increased streamflow, and particularly winter flow peaks. Water temperature is more sensitive to climate warming scenarios than to urbanization and precipitation changes. Future urbanization and climate change together are predicted to significantly increase annual mean streamflow (up to 55%), water temperature (up to 1.9 ºC), TSS load (up to 182%), and TP load (up to 74%).

Sun, Ning↗

Quantifying the cooperative evolution of microphase segregation and nanostructural order in annealed polyurethanes of MDI-BDO-PTHF

Here, we quantify the relationship between microphase segregation and local structure development in thermoplastic polyurethanes. Samples were prepared with varying ratios of 4,40 -methylene diphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) to polytetrahydrofuran (PTHF) and annealed at temperatures T a between RT–140 °C for 20 h each. Distinct populations of smaller and larger ordered domains are distinguished by pair distribution func tion analysis. The intermediate-range order of nanoscale hard domains in the paracrystalline state (form I) is directly extracted and characterized. The results suggest that form I of the MDI-BDO:PTHF system presents a conformational and packing order similar to the form III structure, typically obtained from stretching/annealing, but with limited spatial coherence of 3–7 nm. Heating above T g of the hard segments is necessary to achieve a substantial structural response from the annealing treatment. Increasing T a promotes purification of the soft phase via microphase segregation, coalescence of the hard blocks, and growth of paracrystalline phase, while a minority fraction of longer-range ordered domains left over from production remains relatively constant. We observe a composition-dependent decrease in the average nearest-neighbor dis tance that can be correlated with the greater number of C C, C N, and C O bonds with increased hard segment content. A non-linear deviation in the trend is observed to correlate with sample densification. The mechanical and thermal behavior of the samples is intimately tied to the segregation state.

processing-structure-properties↗

Physical aging and charge transport in poly(3‐hexylthiophene)

The bulk charge transport in a series of regioregular poly(3‐hexylthiophene) materials with different molecular weights (MW) has been studied by the time‐of‐flight technique. Three distinct temperature regions with transitions at ∼60 and ∼140 °C in lower MW material (9.6 kDa), and four regions with an additional transition at ∼180 °C in higher MW material (32.3 kDa) are identified in the temperature dependence of charge carrier mobility and the origin of these transitions is discussed. A pronounced effect of physical aging which reveals as a reversible increase of charge mobility is found. Densification of amorphous phase in‐between the nanocrystals, which reduces the potential energy barriers and provides larger charge transfer integrals, is proposed as an origin of the effect.

Duzhko, Volodimyr V.↗

Synthesis and thermoelectric properties of Cu excess Cu2ZnSnSe4

Quaternary stannites with an excess of copper were successfully synthesized by reacting the constituent elements and subsequent solid state annealing, followed by densification by hot-pressing. The composition for each specimen was confirmed with a combination of Rietveld refinement and elemental analysis. Their high temperature thermoelectric properties were measured from 300 K to 800 K and compared with that of Cu2ZnSnSe4. The thermal conductivity decreases significantly with increasing Cu content at elevated temperatures due to the crystal structure of this material system. A maximum ZT value of 0.86 was obtained at 800 K for the specimen with the highest Cu content, Cu2.2Zn0.8SnSe4.

thermoelectric↗

Recent Progress on Dominant Sulfide‐Type Solid‐State Na Superionic Conductors for Solid‐State Sodium Batteries

Abstract Over the past decade, solid‐state batteries have garnered significant attentions due to their potentials to deliver high energy density and excellent safety. Considering the abundant sodium (Na) resources in contrast to lithium (Li), the development of sodium‐based batteries has become increasingly appealing. Sulfide‐based superionic conductors are widely considered as promising solid eletcrolytes (SEs) in solid‐state Na batteries due to the features of high ionic conductivity and cold‐press densification. In recent years, tremendous efforts have been made to investigate sulfide‐based Na‐ion conductors on their synthesis, compositions, conductivity, and the feasibility in batteries. However, there are still several challenges to overcome for their practical applications in high performance solid‐state Na batteries. This article provides a comprehensive update on the synthesis, structure, and properties of three dominant sulfide‐based Na‐ion conductors (Na 3 PS 4 , Na 3 SbS 4 , and Na 11 Sn 2 PS 12 ), and their families that have a variety of anion and cation doping. Additionally, the interface stability of these sulfide electrolytes toward the anode is reviewed, as well as the electrochemical performance of solid‐state Na batteries based on different types of cathode materials (metal sulfides, oxides, and organics). Finally, the perspective and outlook for the development and practical utilization of sulfide‐based SE in solid‐state batteries are discussed.

Guo, Xiaolin↗

Exploring the Microstructure-Property Relationship of Mg-Al-Mn alloys enhanced via Friction Stir Processing

Friction Stir Processing (FSP) is a solid-state thermomechanical processing technique that enables local grain refinement, densification, and homogenization of microstructure in metallic components. Here, FSP is applied to thin sheets of high-pressure die cast AM60 to address the porosity and heterogeneities inherent to the casting process. In this work, microstructure characterization is correlated to improvements in the static mechanical properties of the Mg-Al-Mn alloy system at various FSP processing conditions. Notably, there is a significant increase in the ductility and ultimate tensile stress of system following FSP. The dominant deformation mechanisms for the as-cast material and the FSP material are investigated. Finally, the fatigue life improvement is correlated to microstructure modifications that may lead to distinct behavior in crack initiation and crack propagation for the as-cast and FSP material.

Garcia, David↗

Solid Phase Processing of Mg-Al-Mn-Ca for High Strength and Ductility

While rare-earth Mg alloys have remarkable properties for high strength applications, lower cost alternatives are necessary for the widespread industry use of Mg. Ca added Mg alloys have shown promise as an alternative to rare-earth alloys. Ca-based precipitates can reduce basal texture, reduce casting porosity, and increase mechanical strength. However, the accumulation of Ca-based precipitates along inter-dendritic regions can severely limit ductility. Here, we apply two solid phase processing techniques, friction stir processing and shear assisted processing and extrusion, to produce wrought microstructure sheet and extruded tubes from a cast Mg-Al-Mn-Ca alloy. Ductility of the alloy is enhanced by densification under applied force and elevated temperature, grain refinement, and refinement of (Al,Mg)-Ca based precipitate.

Garcia, David↗

Characterization and Modeling of Polymeric Foam Under Multi-Axial Static and Dynamic Loading

A polymeric foam commonly used in composite sandwich structures was characterized under multi-axial loading at strain rates varying from quasi-static to dynamic. Additionally, tests were conducted under uniaxial compression, tension, pure shear and combinations of normal and shear stresses. Quasi-static and intermediate strain rate tests were conducted in a servo-hydraulic testing machine. High strain rate tests were conducted using a split Hopkinson pressure bar (Kolsky bar) system made of polycarbonate bars having an impedance compatible to that of the foam material. The typical compressive stress-strain behavior of the polymeric foam exhibits a linear elastic region up to a yield point, a nonlinear elastic-plastic region up to an initial peak or “critical stress” corresponding to collapse initiation of the cells, followed by strain softening up to a local minimum (plateau or saddle point stress) and finally, a strain hardening region up to densification of the foam. The characteristic stresses of the stress-strain behavior vary linearly with the logarithm of strain rate. A general three-dimensional elastic-viscoplastic model, formulated in strain space, was proposed. The model expresses the multi-axial state of stress in terms of an effective stress, incorporates strain rate effects and includes the large deformation region. Stress-strain curves obtained under multi-axial loading at different strain rates were used to develop and validate the elastic-viscoplastic constitutive model. Lastly, excellent agreement was shown between model predictions and experimental results.

36 MATERIALS SCIENCE↗

New insights into the high-pressure polymorphism of SiO[subscript 2] cristobalite

Single-crystal X-ray diffraction experiments with SiO{sub 2} {alpha}-cristobalite reveal that the well-known reversible displacive phase transition to cristobalite-II, which occurs at approximately 1.8 GPa, can be suppressed by rapid pressure increase, leading to an overpressurized metastable state, persisting to pressure as high as 10 GPa. In another, slow pressure increase experiment, the monoclinic high-pressure phase-II was observed to form at {approx}1.8 GPa, in agreement with earlier in situ studies, and its crystal structure has been unambiguously determined. Single-crystal data have been used to refine the structure models of both phases over the range of pressure up to the threshold of formation of cristobalite X-I at {approx}12 GPa, providing important constraints on the feasibility of the two competing silica densification models proposed in the literature, based on quantum mechanical calculations. Preliminary diffraction data obtained for cristobalite X-I reveal a monoclinic unit cell that contradicts the currently assumed model.

Dera, Przemyslaw↗

Mechanical response and microprocesses of reconsolidating crushed salt at elevated temperature

Design, analysis and performance assessment of potential salt repositories for heat-generating nuclear waste require knowledge of thermal, mechanical, and fluid transport properties of reconsolidating granular salt. So, to inform salt repository evaluations, we have undertaken an experimental program to determine Bulk and Young’s moduli and Poisson’s ratio of reconsolidated granular salt as a function of porosity and temperature and to establish the deformational processes by which the salt reconsolidates. Our tests were conducted at 100, 175, and 250 °C. In hydrostatic tests, confining pressure is increased to 20 MPa with periodic unload/reload loops to determine K. Volume strain increases with increasing temperature. In shear tests at 2.5 and 5 MPa confining pressure, after confining pressure is applied, the crushed salt is subjected to a differential stress, with periodic unload/reload loops to determine E and ν. At predetermined differential stress levels the stress is held constant and the salt consolidates. Displacement gages mounted on the samples show little lateral deformation until the samples reach a porosity of ~10 %. Interestingly, vapor is vented only for 250 °C tests and condenses at the vent port. It is hypothesized that the brine originates from fluid inclusions, which were made accessible by heating and intragranular deformational processes including decrepitation. Furthermore, identification and documentation of consolidation processes are inferred from optical and scanning electron microstructural observations. As a result, densification at low porosity is enhanced by water film on grain boundaries that enables solution-precipitation phenomena.

58 GEOSCIENCES↗

Effect of solvent/polymer infiltration and irradiation on microstructure and tensile properties of carbon nanotube yarns

Recently carbon nanotube (CNT) yarns have been gaining importance as an approach to harvest the excellent properties of the CNTs. However, the properties of CNT yarns at this stage are well below the expected value. Investigation of the structure of CNT yarns and possible approaches to enhance the strength and modulus are reported. Scanning electron microscopy and focused ion beam imaging reveal the inherently porous structure and poor orientation, emphasizing the need to enhance packing of CNT bundles in the yarns for increased strength and modulus. Densification of CNT yarn by toluene or polystyrene increases the strength by 140 or 172 % and modulus by 79 or 218 %, respectively, as compared to that of the pristine yarn. E-beam irradiation was investigated as a means to introduce crosslinking and enhanced internanotubes bonding to increase strength and modulus. However, the irradiation resulted in generation of defects and damages to the yarn contributing to reduction in strength and modulus. Raman spectroscopy studies on the irradiated samples reveal the change in bonding characteristics resulting in poor mechanical properties. As a result, denser packing of nanotubes and increased interaction without any damage is the key to improve the properties of CNT yarns.

36 MATERIALS SCIENCE↗

Deformation and damage of sintered low-porosity aluminum under planar impact: microstructures and mechanisms

In this paper, plate impact experiments are conducted to study compaction and spallation of 5% porosity aluminum. Free surface velocity histories, the Hugoniot elastic limit (HEL), and spall strengths are obtained at different peak stresses and pulse durations. Scanning electron microscopy, electron backscatter diffraction, and X-ray computed tomography are used to characterize 2D and 3D microstructures. 3D void topology analyses yield rich information on size distribution, shape, orientation, and connectivity of voids. HEL decreases/increases with sample thickness/impact velocity and approaches saturation. Its tensile strength increases with increasing peak stress and shock-induced densification. With the enhanced compaction under increasing impact velocities, spall damage modes change from growth of original voids to inter-particle crack propagation and to “random” nucleation of new voids. Such a change in damage mechanism also gives rise to a distinct decrease in damage extent at high impact velocities. Finally, compaction induces strain localizations around the original voids, while subsequent tension results in grain refinement, and shear deformation zones between staggered cracks.

36 MATERIALS SCIENCE↗

Study on Microwave Performance of Low-Temperature Sintered, Ba(CoTi){sub 1.5}Fe{sub 9}O{sub 19} Ferrite for Application at UHF Frequency

M-type barium ferrite, Ba(CoTi){sub 1.5}Fe{sub 9}O{sub 19}, was synthesized via the solid-state reaction method. BBSZ, i.e., B{sub 2}O{sub 3} −Bi{sub 2}O{sub 3} −SiO{sub 2} −ZnO, was added to adjust the sintering temperature to values lower than that of silver (i.e., ∼961 °C). The phase formation characteristics, microstructure, magnetic, and microwave properties were characterized by x-ray diffraction, scanning electron microscope, vibrating sample magnetometer, and impedance analyzer, respectively. The results show that densification of samples were enhanced by increasing the amount of BBSZ with corresponding gains realized in magnetic properties. Such enhanced properties in Ba(CoTi){sub 1.5}Fe{sub 9}O{sub 19} are attributed to the low-melting point experienced as the result of BBSZ glass additives which gave rise to the stabilization of a liquid phase during sintering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗