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At least 415 records · Page 23

Scaling microstructural processes in the sintering of ionic ceramics

A multi-scale framework, combining a multiphase field formulation and large deformation mechanics, was developed as a stepping stone to perform the data analytics of the microstructural level kinetics of a sintering solid. Relevant microstructural information from this framework, such as grain, stress, and porosity statistics, was scaled up to describe the macroscopic level sintering kinetics. Here, the developed formulation was applied to describe the electric field assisted sintering of Y 2 O 3 . Microstructural inhomogeneities in a multi-granular solid result in the formation of a field of compressive stress networks, which interleave with low compression and weakly tensile regions, defining a scaffolding for sintering concentration regions to develop. A Poisson effect-induced lateral stress network is also naturally self-induced as a result of the mechanical constraints imposed by the sintering apparatus. For long sintering times, localized shear stresses enhancing mass flow along grain boundaries and internal surfaces develop. Three-sided pores are removed by either vacancy transport to the surrounding pores, or move towards the external surfaces through grain boundary diffusion. Four- and higher order-sided pores stabilize because an equal amount of vacancies are gained and lost through the connecting grain boundaries. Grain dewetting contributes to pore coalescence, suggesting that pore kinetics and grain growth are coupled and should be analyzed in concert. The combined sintering and grain growth kinetics define six regimes of sintering behavior: (1) T, the transient regime; (2) E$_Υ$, the surface energy dominated, early sintering regime, where the grain growth exponent, p = 1, and the stress concentration factor, $f$ ~ $1/\hat{ρ}^{4.6}$; (3) E S , the stress dominated, early sintering regime, where p = 1 and $f$ ~ $1/\hat{ρ}^{4}$; (4) I$_Υ$, the surface energy dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4.6}$; (5) I S , the stress dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4}$; and (6) L, the late sintering regime, where p = 3 and $f$ ~ 1. At the macroscopic level, the rapid densification and suppression of grain growth observed in the electric field assisted sintering process is a consequence of the compounding effects of the underlying stress-, transport-, and interfacial-energy-induced energy minimization kinetics, as predicted by the multi-scale framework.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Aligned Carbon Nanotube Reinforced Silicon Carbide Composites by Chemical Vapor Infiltration

Owing to their exceptional stiffness and strength1 4, carbon nanotubes (CNTs) have long been considered to be an ideal reinforcement for light-weight, high-strength, and high-temperature-resistant ceramic matrix composites (CMCs)5 10. However, the research and development in CNT-reinforced CMCs have been greatly hindered due to the challenges related to manufacturing including poor dispersion, damages during dispersion, surface modification, densification and sintering, weak tube/matrix interfaces, and agglomeration of tubes at the matrix grain boundaries5,11. Here we report the fabrication of high-quality aligned CNT/SiC composites by chemical vapor infiltration (CVI), a technique that is being widely used to fabricate commercial continuous-filament CMCs12 15. Using the CVI technique most of the challenges previously encountered in the fabrication of CNT composites were readily overcome. Nanotube pullouts, an important toughening mechanism for CMCs, were consistently observed on all fractured CNT/SiC samples. Indeed, three-point bending tests conducted on individual CNT/SiC nanowires (diameters: 50 200 nm) using an atomic force microscope show that the CNT-reinforced SiC nanowires are about an order of magnitude tougher than the bulk SiC. The tube/matrix interface is so intimate and the SiC matrix is so dense that a ~50-nm-thick SiC coating can effectively protect the inside nanotubes from being oxidized at 1600 C in air. The CVI method may be extended to produce nanotube composites from a variety of matrix

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Development of mesopores in superfine grain graphite neutron-irradiated at high fluence

Microstructural changes induced by neutron irradiation of superfine grain graphite G347A (Tokai Carbon, Japan) were examined by nitrogen adsorption at 77 K and by three microscopy techniques (SEM, TEM and FIB-SEM tomography). The specimens were irradiated at doses of up to 30 dpa, covering stages before and after the turnaround fluence at three temperatures (300, 450, 750 °C) of their irradiation envelope. The initial graphite densification at low fluences did not produce any detectable effect in the pore size range (<350 nm) measured by gas adsorption. However, graphite irradiated at high fluences, after turnaround, showed severe structural changes. At all three temperatures and high irradiation fluences, gas adsorption revealed significant increase of the volume of narrow mesopores (<5–20 nm) and up to five times increase of BET surface area, both in linear relationship with the relative volume expansion. Analysis of microscopy images showed multiplication of fine macropores (>50 nm) at high irradiation fluences and more structural changes on multiple scales, from nanometers to microns. As a result, this work demonstrates the unique ability of gas adsorption techniques to analyze open pores with sizes between sub-nanometer and sub-micron in bulk nuclear graphite, with supporting microscopy results.

36 MATERIALS SCIENCE↗

Microstructural and bulk property changes in hardened cement paste during the first drying process

This paper reports the microstructural changes and resultant bulk physical property changes in hardened cement paste (hcp) during the first desorption process. The microstructural changes and solid-phase changes were evaluated by water vapor sorption, nitrogen sorption, ultrasonic velocity, and {sup 29}Si and {sup 27}Al nuclear magnetic resonance. Strength, Young's modulus, and drying shrinkage were also examined. The first drying process increased the volume of macropores and decreased the volume of mesopores and interlayer spaces. Furthermore, in the first drying process globule clusters were interconnected. During the first desorption, the strength increased for samples cured at 100% to 90% RH, decreased for 90% to 40% RH, and increased again for 40% to 11% RH. This behavior is explained by both microstructural changes in hcp and C–S–H globule densification. The drying shrinkage strains during rapid drying and slow drying were compared and the effects of the microstructural changes and evaporation were separated.

36 MATERIALS SCIENCE↗

Effect of pulverized fuel ash and CO{sub 2} curing on the water resistance of magnesium oxychloride cement (MOC)

This paper presents a study on the use of pulverized fuel ash (PFA) to improve the water resistance of magnesium oxychloride cement (MOC). Strength retention coefficients and volume stability were tested to evaluate the water resistance of MOC, in which the addition of PFA resulted in a remarkable improvement. The characterization of hydration products before and after water immersion was carried out using quantitative X-ray diffraction (QXRD), thermogravimetric (TG), Fourier-transformed infrared spectroscopy (FTIR) and scanning electron microscope (SEM). With the Q-XRD analysis, it was shown that the addition of PFA could result in the great increase of the amount of amorphous phase during air curing. This amorphous gel was identified as a mixture of magnesium-chloride-silicate-hydrate gel (M-Cl-S-H gel) and magnesium-chloride-hydrate gel (M-Cl-H gel) by elemental mapping scanning. It suggested that PFA could not only react with MOC to form M-Cl-S-H gel, but also change the morphology of magnesium oxychloride. The generation of insoluble M-Cl-S-H gel and M-Cl-H gel and densification of the microstructure contributed to the improvement of the water resistance of MOC. The MOC mortar expanded during air curing due to the hydration of excess MgO. Water immersion led to more expansion of MOC mortar as a result of the continuously hydration of excess MgO and the formation of Mg(OH){sub 2}. Adding PFA could increase the expansion of MOC mortar during air curing, which may because the amorphous gel could remain more water and benefit to the hydration of MgO. While, the addition of PFA could decrease the expansion of cement mortar during water immersion perhaps due to the reduction of the content of excess MgO and the insoluble amorphous-gel-layer that protect the MgO from hydration. Moreover, CO{sub 2} curing could further improve the performance of the PFA-blended MOC due to the formation of a higher content of amorphous gel.

36 MATERIALS SCIENCE↗

Application of organic- and nanoparticle-modified foams in foamed concrete: Reinforcement and stabilization mechanisms

Highlights: • An ultra-stable foam was fabricated by modifying the gas–liquid interface. • A homogeneous and finer pore structure of foamed concrete was generated. • Stabilization and enhancement mechanisms were investigated. - Abstract: In this study, an ultra-stable foam used for foamed concrete was fabricated by modifying the gas–liquid interface by coupling the effects of an organic surfactant and nanoparticles. A serial of techniques was employed to study the products and microstructure development of foam and foamed concrete, respectively. The results show that nano-silica and hydroxypropyl methylcellulose can slow the coalescence and disproportionation of the bubbles by adsorbing at the air bubble surface and increasing the viscosity of cell wall paste, thus preventing gas transfer and hindering physical drainage between the gaseous and liquid phases. Also, a more homogeneous and finer pore structure is generated with the inclusion of the organic surfactant and nanoparticles. The pozzolanic reaction between the nano-silica and Ca(OH){sub 2} results in an increased C-S-H content and the densification of the cell wall structure. In addition, the stability of foamed concrete with modification and relevant stabilization mechanisms were also investigated.

36 MATERIALS SCIENCE↗

Effects of anionic and nonionic surfactants on the dispersion and stability of nanoSiO2 in aqueous and cement pore solutions

It has been well recognized that the benefits and effectiveness of nanoparticles in cement-based materials could not be maximized if these are not well dispersed. To address this issue, in this study, different anionic (SDS and PCE) and nonionic surfactants (Tweens and Tritons) were used to disperse nanosilica (NS) in aqueous solution and cement pore solution. The results show that the dispersibility of NS in cement pore solution was improved, and the compressive strength of the cement-NS pastes increased linearly with critical micelle concentration (CMC) of nonionic surfactants. Among all surfactants studied, Triton X-405 led the paste to the highest increase in strength (33% at 1-day and 41% at 3-days) since it had the highest CMC. TEM and EDS analysis evidenced that this strength increase might be attributed to the nucleation of outer product CSH gel and its densification with calcite nanocrystals, attributed to Triton X-405 addition.

36 MATERIALS SCIENCE↗

Effects of carbonation on the retention of heavy metals in chemically activated BOF slag pastes

Basic Oxygen Furnace slag contains heavy metals, including vanadium, chromium and molybdenum. The leachability of these elements determines the industrial applicability of slag-based building products. This study investigates the post‑carbonation leaching of heavy metals from activated BOF slag pastes with the focus on the activator dosage and type (sodium and potassium citrate). Results reveal that the high degree of brownmillerite hydration boosts the leachability of heavy metals as its hydration product- hydrogarnet is less stable upon carbonation. With two leaching procedures, it is demonstrated that the carbonation resistance of pastes becomes the main attribute in preventing the leaching of heavy metals. It can be enhanced by optimising the activator dosage to facilitate the hydration of C{sub 2}S and consequent structural densification.

36 MATERIALS SCIENCE↗

Influence of supplementary cementitious materials on microstructure and transport properties of spacer-concrete interface

Reinforcement spacers are a critical component of concrete structures. Their presence affects microstructure and transport properties of concrete cover though this is not widely appreciated. This paper presents the first study to determine whether the negative effects of spacers can be mitigated through the use of supplementary cementitious materials such as silica fume, fly ash and blast-furnace slag. Concrete samples (>200) with different spacers, binders, curing and drying regimes were prepared and tested for diffusion, permeation, absorption, electrical conductivity, carbonation and microstructure. It was found that spacers increase all transport properties, the extent depending on type of spacer, drying regime and transport mechanism. The spacer-concrete interface is weak, porous and micro-cracked, and this lowers the resistance of concrete to ingress of aggressive agents. The beneficial effects of SCMs (strength enhancement and densification) and prolonged curing (120-day) are insufficient to overcome the negative effects of spacers. Implications for durability are discussed.

36 MATERIALS SCIENCE↗

Compositional inhomogeneityand segregation in (K 0.5 Na 0.5 )NbO 3 ceramics

The effects of the calcination temperature of (K 0.5 Na 0.5 )NbO 3 (KNN) powder on the sintering and piezoelectric properties of KNN ceramics have been investigated in this report. KNN powders are synthesized via the solid-state approach. Scanning electron microscopy and X-ray diffraction characterizations indicate that the incomplete reaction at 700 °C and 750 °C calcination results in the compositional inhomogeneity of the K-rich and Na-rich phases while the orthorhombic single phase is obtained after calcination at 900 °C. During the sintering, the presence of the liquid K-rich phase due to the lower melting point has a significant impact on the densification, the abnormal grain growth and the deteriorated piezoelectric properties. From the standpoint of piezoelectric properties, the optimal calcination temperature obtained for KNN ceramics calcined at this temperature is determined to be 800 °C, with piezoelectric constant d 33 =128.3 pC/N, planar electromechanical coupling coefficient k p =32.2%, mechanical quality factor Q m =88, and dielectric loss tan δ=2.1%.

36 MATERIALS SCIENCE↗

In-situ observation of oxygen mobility and abnormal lattice expansion in ceria during flash sintering

Flash sintering has been shown to be an effective method of sintering for many types of ceramics. However, the characteristics of flash sintering for each type of ceramic varies. When ionically conducting ceramics are sintered under a DC electric field, a strong dependence of densification with respect to position is observed. Microstructural analysis of the effect of electric field on oxygen ion conductors shows non-stoichiometry (oxygen deficiency) at the cathode which continues to build up over time under flash. In oxygen ion conductors, dominant charge carriers during flash are oxygen ions and the final density of the specimen is related to the availability of oxygen. This effect is no longer evident when using an AC power supply. In conclusion, use of AC instead of DC electric field is preferable for flash sintering of ionically conducting ceramics.

36 MATERIALS SCIENCE↗

Insight into the BiFeO 3 flash sintering process by in-situ energy dispersive X-ray diffraction (ED-XRD)

The sintering mechanism of BiFeO 3 has been investigated in-situ by energy dispersive X-ray diffraction (ED-XRD) using a high-energy white collimated X-ray beam from the Advanced Photon Source (Argonne National Laboratories). Such radiation is very penetrating thereby allowing measurements of the sample even when placed inside the flash sintering set up. Additionally, the fast ED-XRD measurements permit monitoring the flash sintering process by providing information about phase composition and sample temperature in real time. Moreover, profile scans, obtained by moving the stage vertically while recording the ED-XRD spectra, permit investigating the homogeneity of the flash for the entire length of the sample. All experiments have been complemented by ex-situ studies. Here, it has been concluded that flash sintering of BiFeO 3 is a homogeneous process without any directionality effects. Furthermore, flash sintering takes place at quite low temperatures (below the Tc ≈ 830 °C), which may be related to the high quality of the samples, as pure, highly insulating ceramics without evidence of secondary phases with a homogenous nanostructured grain size distribution are obtained by this technique. Moreover, it is also evidenced that the rapid heating of the sample does not seem to justify, at least by itself, the densification process. Therefore, it appears that the electric current should play a role in the enhanced mobility during the sintering process.

36 MATERIALS SCIENCE↗

Development of a silicon carbide ceramic based counter-flow heat exchanger by binder jetting and liquid silicon infiltration for concentrating solar power

A silicon carbide ceramic counter-flow heat exchanger with integrated headers was printed by binder jetting additive manufacturing process. Multiple phenolic binder infiltration cycles (3 or 5) followed by pyrolysis were conducted to increase the net carbon content of the printed SiC specimens. Subsequently, to attain full densification, silicon melt infiltration was used. The microstructure and mechanical properties were comprehensively characterized on the densified material. The chemical compositions and visual distribution of the various regions in the specimens were determined via scanning electron microscopy, while X-ray diffraction and synchrotron µ-computed tomography were used to provide a quantitative assessment of the volume fractions of the identified phase regions. Microhardness measurements showed dependence on the local microstructure. The fracture strength of the material was correlated with the specimen density and agreed with the reported values in the literature. High-temperature exposure at 750 °C for up to 200h did not degrade the strength for the specimens with three phenolic-binder infiltrations; however, the strengths degraded for ones with five phenolic-binder infiltrations. The associated fracture toughnesses of the specimens were ~3.4 MPam 1/2 at room temperature and 750°C, and the thermal conductivities varied from >150 W/mK at room temperature to ~45 W/mK at 750°C. Hence, this study validated the use of the binder-jetting printed SiC ceramic materials for high-temperature heat exchanges. Lastly, we also present in this work the first successful fabrication of a binder-jetting printed one-piece dense SiC ceramic heat exchanger body with unblocked channels that can be used for the flow of heat transfer fluids.

36 MATERIALS SCIENCE↗

Predicting oxidation damage of ultra high-temperature carbide ceramics in extreme environments using machine learning

Determining the oxidation resistance of UHTC carbides in extreme environments is challenging theoretically and experimentally due to the high dimensional complexity of influencing variables and intricate testing setups. Herein we demonstrate the use of machine learning (ML) models trained with experimental literature data to predict the oxide thickness of UHTC carbides exposed to air based on composition, mean grain size, relative densification, holding time, and temperature. A multi-dimensional database with 76 occurrences is created containing experimental results of Hf, Zr, and Ta carbides plus additives. In this study, the preprocessed database is then used to train ML models to predict their oxidation behavior. The trained model predicts the oxidation damage in the form of an average oxide thickness in UHTC carbides with a Mean Absolute Error (MAE) of ±65.45 μm for samples in the testing set that developed thicknesses up to 1000 μm. The model successfully predicted oxidation damage for a recession rate lower than 60 μm/min. It is noticed that the ensemble method MAE is increased to ±134.34 μm while forecasting the oxidation of samples with a recession rate higher than the threshold. The unprecedented approach is a novel way to predict the damage through the oxidation of carbide compounds before processing for a smarter design with room for improvement.

36 MATERIALS SCIENCE↗

Physicochemical properties of digital light processing 3D-Printed alumina and mullite ceramics

Alumina ceramics fabricated using conventional techniques such as uniaxial pressing or injection molding are popular due to their low density, excellent insulation, and mechanical properties. However, these methods often limit the fabrication of complex geometries with high dimensional accuracy due to tooling constraints and limited design freedom. To overcome these limitations, this study employed Digital Light Processing (DLP) additive manufacturing (AM), which enables the production of precise structures. In addition, the optimization of sintering parameters to enhance the densification and performance of alumina and mullite ceramics was investigated, with a specific focus on how varying sintering temperatures and hold times affect part shrinkage, geometric accuracy, and material integrity. Flexural strength of both alumina and mullite specimens was clearly influenced by the way the layers was stacked. When layers were arranged across the direction of the applied load (Z = 4; XZ), the strength was higher than when they were stacked along the same direction as the load (Z = 3; XY). Weibull analysis based on these results showed high modulus values across all samples, indicating good reliability in the flexural strength measurements. This reliability, combined with the clear influence of sintering parameters, highlights how processing conditions effect the material properties and mechanical performance of parts produced through DLP additive manufacturing. In conclusion, these findings open new avenues for ceramic AM across various applications, enhancing the potential for innovation in fields such as aerospace, biomedical engineering, and energy.

36 MATERIALS SCIENCE↗

Sol-gel processing of a covalent organic framework for the generation of hierarchically porous monolithic adsorbents

Covalent organic frameworks (COFs) have emerged as a versatile material platform for such applications as chemical separations, chemical reaction engineering, and energy storage. Their inherently low mechanical stability, however, frequently renders existing methods of pelletization ineffective, contributing to pore collapse, pore blockage, or insufficient densification of crystallites. Here, we present a process for the shaping and densifying of COFs into robust centimeter-scale porous monoliths without the need for templates, additives, or binders. This process minimizes mechanical damage from shear-induced plastic deformation and further provides a network of interparticle mesopores that we exploit in accessing analyte capacities above those achievable from the intrinsic COF structure. Using a lattice-gas model, we accurately capture the monolithic structure across the mesoporous range and tie pore architecture to performance in both gas-storage and -separation applications. Collectively, these results represent a substantial step in the practical applicability of COFs and other mechanically weak porous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Instabilities and phase transitions in architected metamaterials: a gradient-enhanced continuum approach

Architected metamaterials such as foams and lattices exhibit a wide range of properties governed by microstructural instabilities and emerging phase transitions. Their macroscopic response–including energy dissipation during impact, large recoverable deformations, morphing between configurations, and auxetic behavior–remains difficult to capture with conventional continuum models, which often rely on discrete approaches that limit scalability. In this work, we propose a nonlocal continuum formulation that captures both stable and unstable responses of elastic architected metamaterials. The framework extends anisotropic hyperelasticity by introducing nonlocal variables and internal length scales reflective of microstructural features. Local polyconvex free-energy models are systematically augmented with two families of non-(poly)convex energies, enabling both metastable and bistable responses. Implementation in a finite element framework enables solution using a hybrid monolithic–staggered strategy. Simulations capture densification fronts, forward and reverse transitions, hysteresis loops, imperfection sensitivity, and globally coordinated auxetic modes. Overall, this framework provides a robust foundation for accelerated modeling of instability-driven phenomena in architected metamaterials, while enabling extensions to anisotropic, dissipative, and active systems as well as integration with data-driven and machine learning approaches.

42 ENGINEERING↗