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TEM Analysis of Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

Silicon Carbide (SiC) is a promising material for thermostructural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, Mo-B and TiCu. In this presentation, we report the microstructure of diffusion bonded SA-THX mainly with TiCu interlayers obtained by TEM observations, and the influence of metallic interlayers on the joint microstructure and microhardness will be discussed.

Ceramics

The Effect of Interlayer Delay on the Heat Accumulation, Microstructures, and Properties in Laser Hot Wire Directed Energy Deposition of Ti-6Al-4V Single-Wall

Laser hot wire directed energy deposition (LHW-DED) is a layer-by-layer additive manufacturing technique that permits the fabrication of large-scale Ti-6Al-4V (Ti64) components with a high deposition rate and has gained traction in the aerospace sector in recent years. However, one of the major challenges in LHW-DED Ti64 is heat accumulation, which affects the part quality, microstructure, and properties of as-built specimens. These issues require a comprehensive understanding of the layerwise heat-accumulation-driven process–structure–property relationship in as-deposited samples. In this study, a systematic investigation was performed by fabricating three Ti-6Al-4V single-wall specimens with distinct interlayer delays, i.e., 0, 120, and 300 s. The real-time acquisition of high-fidelity thermal data and high-resolution melt pool images were utilized to demonstrate a direct correlation between layerwise heat accumulation and melt pool dimensions. The results revealed that the maximum heat buildup temperature of the topmost layer decreased from 660 °C to 263 °C with an increase to a 300 s interlayer delay, allowing for better control of the melt pool dimensions, which then resulted in improved part accuracy. Furthermore, the investigation of the location-specific composition, microstructure, and mechanical properties demonstrated that heat buildup resulted in the coarsening of microstructures and, consequently, the reduction of micro-hardness with increasing height. Extending the delay by 120 s resulted in a 5% improvement in the mechanical properties, including an increase in the yield strength from 817 MPa to 859 MPa and the ultimate tensile strength from 914 MPa to 959 MPa. Cooling rates estimated at 900 °C using a one-dimensional thermal model based on a numerical method allowed us to establish the process–structure–property relationship for the wall specimens. The study provides deeper insight into the effect of heat buildup in LHW-DED and serves as a guide for tailoring the properties of as-deposited specimens by regulating interlayer delay.

36 MATERIALS SCIENCE

All‐Solid‐State Lithium–Sulfur Batteries of High Cycling Stability and Rate Capability Enabled by a Self‐Lithiated Sn‐C Interlayer

Abstract All‐solid‐state lithium–sulfur batteries (ASSLSBs) have attracted intense interest due to their high theoretical energy density and intrinsic safety. However, constructing durable lithium (Li) metal anodes with high cycling efficiency in ASSLSBs remains challenging due to poor interface stability. Here, a compositionally stable, self‐lithiated tin (Sn)‐carbon (C) composite interlayer (LSCI) between Li anode and solid‐state electrolyte (SSE), capable of homogenizing Li‐ion transport across the interlayer, mitigating decomposition of SSE, and enhancing electrochemical/structural stability of interface, is developed for ASSLSBs. The LSCI‐mediated Li metal anode enables stable Li plating/stripping over 7000 h without Li dendrite penetration. The ASSLSBs equipped with LSCI thus exhibit excellent cycling stability of over 300 cycles (capacity retention of ≈80%) under low applied pressure (<8 MPa) and demonstrate improved rate capability even at 3C. The enhanced electrochemical performance and corresponding insights of the designed LSCI broaden the spectrum of advanced interlayers for interface manipulation, advancing the practical application of ASSLSBs.

Ye, Lei

Disentangling interlayer confinement and pore surface adsorption in functionalized smectites for tunable ethylene gas capture

Smectite-based adsorbents are increasingly being studied as sustainable packaging materials for scavenging ethylene, a plant hormone that accelerates fruit ripening. However, the mechanisms governing their uptake and retention remain poorly understood. Here, to tackle this question we systematically investigate ethylene gas-solid interactions in pristine, acid-activated, and choline-functionalized montmorillonites using a complementary combination of structural, gravimetric, and spectroscopic techniques, including inelastic neutron scattering. We experimentally distinguish ethylene populations associated with interlayer confinement, mesopore, and external surface adsorption. We show that chemical functionalization distinctly controls adsorption pathways: acid activation enhances total uptake by generating mesoporous adsorption sites and promoting partial interlayer intercalation, yielding capacities comparable to those of leading smectite-based adsorbents, while choline functionalization promotes preferential confinement and stabilization of guest molecules within the interlayer galleries. Advanced spectroscopic analysis provides molecular-level insight into confinement environments and interaction strengths. We also establish clear structure-property relationships by correlating uptake values derived from independent techniques, linking chemical modification, accessible adsorption domains, and retention behavior. These findings provide general design principles for tuning gas-solid interactions in functionalized layered silicates and highlight their potential as adaptable platforms for sustainable ethylene gas capture and selective adsorption technologies.

Ethylene adsorption mechanism

Plastic-waste hydrogenolysis over two-dimensional MXene-supported ruthenium catalysts with tunable interlayer spacing

The hydrogenolysis of plastics is limited by active-site inaccessibility and inefficient mass transport of bulky polymer chains. To overcome these challenges, this work developed two-dimensional MXene-supported Ru (Ru@MXene) catalysts. Lyophilization of a solution containing dispersed MXene sheets and Ru precursors enabled the confinement of Ru species within the MXene interlayers, which act as pillars to expand the interlayer spacing. Building on this, a silica-pillared MXene-supported Ru (Ru@P-MXene) with even larger interlayer spacing exhibited a reaction rate of 914.9 g C5–C35 g Ru –1 h –1 for the hydrogenolysis of low-density polyethylene (LDPE) into valuable liquid chemicals (e.g., C 5 –C 35 ). A comparison of product yields between Ru@P-MXene and Ru@MXene suggests that elongated Ru particles confined within the MXene support expose their side facets for the reaction. In conclusion, this work demonstrates a new application of MXene in thermochemical catalysis, offering a solution to the challenges of active-site accessibility, mass transport, and reaction confinement in chemical plastic upcycling.

2D materials

Tuning the interlayer coupling in La 0.7 Sr 0.3 Mn 0.95 Ru 0.05 O 3 / LaNiO 3 multilayers with perpendicular magnetic anisotropy

In ferromagnetic oxide epitaxial multilayers, magnetic properties and interlayer coupling are determined by a variety of factors. Beyond the contribution of interlayer exchange coupling, strain and interfacial effects, such as structural reconstructions or charge transfer, play significant roles, resulting in complex magnetic behavior. In this study, the interlayer coupling of ferromagnetic La 0.7 ⁢Sr 0.3⁢ Mn 0.95 ⁢Ru 0.05 ⁢O 3 (LSMRO) layers (8 nm thick) was investigated, when separated by epitaxial spacers of paramagnetic metallic LaNiO 3 (LNO), in stacks exhibiting perpendicular magnetic anisotropy. By varying the thickness of the spacer, it was found that the coupling between two LSMRO layers changes from antiferromagnetic (with a 4-unit-cell-thick LNO spacer) to ferromagnetic (with a 6-unit-cell-thick LNO spacer). For multilayers comprising five LSMRO layers and a 4-unit-cell-thick LNO spacer, the antiferromagnetic coupling was preserved. However, the effective magnetic anisotropy changed, causing the magnetization to cant more towards the in-plane direction. Further, this behavior was corroborated by X-ray magnetic circular dichroism (XMCD) investigations at the Mn and Ni L 3 edges. The XMCD results indicated that the 4-unit-cell-thick LNO spacer in the multilayer become magnetically ordered, closely following the magnetization of adjacent LSMRO layers.

36 MATERIALS SCIENCE

Porous Interlayers that Getter Surface-Segregating Species for Improved Silver Wetting, Adhesion, and Electrical Contact on Stainless Steel SOFC Components

Here, porous nickel interlayers or porous platinum interlayers were shown to promote the wetting, spreading, and adhesion of silver on alumina-forming ferritic stainless steel (AFFSS) and chromia-forming ferritic stainless steel (CFFSS). These interlayers resulted in dense, crack-free AFFSS|Ag-Ni|CFFSS and AFFSS|Ag-Pt|CFFSS braze joints that, after 300 h in 650 °C air, displayed shear strengths up to 70 MPa similar to, or larger than, those of AFFSS|Ag-CuO|CFFSS or AFFSS|Ag|CFFSS joints subjected to identical treatment. Similarly, after exposure to 25 cycles of (50 switches between) 12 h of 650 °C air and 12 h of 650 °C 4%H 2 –96%N 2 , AFFSS|Ag-Ni|CFFSS and AFFSS|Ag-Pt|CFFSS braze joints displayed shear strengths significantly larger than those of AFFSS|Ag-CuO|CFFSS or AFFSS|Ag|CFFSS joints subjected to identical treatment. In addition, nickel and platinum were found to chemically getter surface-segregating steel constituents, particularly Al from the AFFSS. As a result, Ag-Ni and Ag-Pt electrical contact resistances on AFFSS and CFFSS substrates were several orders of magnitude lower than those of conventional Ag-CuO reactive air brazes or Heraeus C8710 Ag contact pastes. Together, these results suggest that Ag-Pt and especially Ag-Ni may be useful for the fabrication of durable joints, seals, and/or electrical contacts in electrical/electrochemical devices exposed to high temperatures and/or variable oxygen partial pressure environments.

36 MATERIALS SCIENCE

Joining of materials with engineered interlayers

A reliable method to join a variety of different materials is developed which uses engineered coatings to produce strong bonds by solid-state techniques at low temperatures (300-400 C). The strong bonds are capable of accommodating the strains created between Si and most substrates due to differences in thermal expansion coefficients. The approach encompasses two phases: noble metal compliant interlayers and functionally gradient interlayer bonding. Preliminary results are presented and the Ag interlayer bonds are microstructurally characterized confirming that the planar magnetron sputtered coatings/bonds are fully dense and metallurgically sound.

Challenger, Kenneth D.

TEM Observation of the Ti Interlayer Between SiC Substrates During Diffusion Bonding

Diffusion bonding was carried out to join SiC to SiC substrates using titanium interlayers. In this study, 10 m and 20 m thick physical vapor deposited (PVD) Ti surface coatings, and 10 and 20 m thick Ti foils were used. Diffusion bonding was performed at 1250 C for PVD Ti coatings and 1200 C for Ti foil. This study investigates the microstructures of the phases formed during diffusion bonding through TEM and selected-area diffraction analysis of a sample prepared with an FIB, which allows samples to be taken from the reacted area. In all samples, Ti3SiC2, Ti5Si3Cx and TiSi2 phases were identified. In addition, TiC and unknown phases also appeared in the samples in which Ti foils were used as interlayers. Furthermore, Ti3SiC2 phases show high concentration and Ti5Si3Cx formed less when samples were processed at a higher temperature and thinner interlayer samples were used. It appears that the formation of microcracks is caused by the presence of intermediate phase Ti5Si3Cx, which has anisotropic thermal expansion, and by the presence of an unidentified Ti-Si-C ternary phase with relatively low Si content.

Tsuda, Hiroshi

TEM Analysis of Interfaces in Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

Silicon Carbide (SiC) is a promising material for thermo-structural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, and Mo-B. In this presentation, the result of microstructural analysis obtained by TEM observations and the influence of metallic interlayers and fiber orientation of SA-THX on the joint microstructure will be discussed.

Silicon Carbide

Alloying Interlayers for Anode‐Less Lithium‐Metal Polymer Batteries

Anode‐less lithium‐metal batteries potentially offer further increased energy densities. However, the Coulombic efficiency (CE) of lithium plating and stripping, as a classical measure of Li inventory reversibility, is commonly still insufficient for achieving long‐lasting rechargeable batteries. Herein, the potential benefits of employing thin (20 nm) metal interlayers of Ag, Pt, and Au on Cu to alloy with Li in Cu||Li half‐cells and induce homogeneous Li plating with poly(ethylene oxide)‐based electrolytes are investigated. Interestingly, not all alloying interlayers enable a higher CE compared to neat Cu foil with 84%—specifically Ag@Cu with only 81%, while the best performing one, Au@Cu, provides a substantially increased CE of 91%. While generally the formation of “dead lithium” is found to be the major source of CE, this appears to be less pronounced in the case of Au@Cu, indeed. Further improvement can be achieved by carefully adjusting the cell voltage to a region in which the continuous de‐/alloying is suppressed, yielding a further enhanced CE of 94%, thus highlighting the need for a comprehensive approach to design suitable electrode chemistries and designs beyond a “simple” material improvement.

anode-less battery

Expanding the interlayer spacing of MXene through nanoarchitecture design

MXenes, a diverse class of two-dimensional transition metal carbides and nitrides with distinct surface chem istries, offer remarkable electrochemical and physicochemical properties. Yet, their performance can be hindered by the intrinsic restacking of layers, which restricts surface activity. This review outlines recent advances in interlayer spacing modulation strategies designed to overcome this limitation. A wide range of guest spe cies–including mono- and polyatomic ions, small molecules, low-dimensional nanomaterials, and polymers–are discussed with respect to their intercalation mechanisms, structural effects, and capacity to introduce functional enhancements. These intercalating species interact with MXene via electrostatic forces, hydrogen bonding, redox reactions, or covalent linkages, resulting in stable, expanded nanoarchitectures. The influence of expanded spacing on capacitive behavior is briefly highlighted to illustrate its practical relevance. Although Ti 3 C 2 T x is currently the most extensively investigated MXene, applying these interlayer engineering strategies to other MXene compositions will be essential for accessing a wider range of properties and functionalities.

36 MATERIALS SCIENCE

Transparent and Conductive Polyimide‐Ionene Hybrid Interlayers for High Performance and Cost‐Effective Semitransparent Organic Solar Cells

The contradiction between high transmittance and favorable conductivity poses a great challenge in developing effective cathode interlayer (CIL) materials with sufficient thickness tolerance, which hinders the further advancement of organic solar cells (OSCs). Herein, a completely new class of alcohol processable polyimide-ionene hybrids (PIIHs) is proposed by melding pyromellitic diimide (PMD) subunits into imidazolium-based ionenes backbone covalently. These PIIHs, named PMD-DI and PMD-PD, boast high transparency, suitable energy levels, and decent conductivity. A higher PMD content endows PMD-PD with improved work function tunability, electrical properties, and crystallinity, enabling PMD-PD as CIL material with excellent thickness-insensitive characteristics, while simultaneously improving device stability significantly. Furthermore, PMD-PD also exhibits good compatibility with various electrodes and active layers, offering solar cell efficiencies of up to 19.91% and 19.29% with Ag and Cu cathodes, respectively. More importantly, the application of PMD-PD can improve the performance of semi-transparent OSCs without losing transmittance, thereby drastically enhancing the light utilization efficiency to 4.04% with an ultrathin, low-cost Cu cathode, that competes with leading optical modulation-free semitransparent OSCs with expensive Ag cathodes. This work opens a pathway to realize transparent and conductive interlayers by strategic molecular design, leading to highly efficient, stable, and cost-effective OSCs suitable for diverse applications.

You, Zuhao

Interlayer Design for Halide Electrolytes in All‐Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state lithium‐metal batteries (ASSLMBs) are promising for transportation electrification due to their superior safety and high energy density. Lithium halide electrolytes provide excellent processing flexibility, high ionic conductivity, and anodic stability (>4.1 V), making them highly compatible with high‐voltage cathodes, surpassing sulfide electrolytes (<2.1 V). Nevertheless, halide electrolytes suffer from low cathodic stability and form an electronically conductive interphase with lithium, resulting in a critical current density (CCD) of nearly zero. Herein, Li 3 YbCl 6 electrolytes are synthesized that are kinetically stable with lithium by forming an electronic insulating solid electrolyte interphase. Guided by critical overpotential criteria, a PI 3 interlayer is designed that transforms into Li 6 PI 3 upon contact with lithium, substantially reducing the interfacial resistance of Li 3 YbCl 6 against lithium to 34 Ω and achieving a high critical overpotential of 114 mV. By substituting Yb with Lu, Li 3 LuCl 6 electrolytes with Li 6 PI 3 interlayers reach a CCD of 1.0 mA cm −2 at a capacity of 1.0 mAh cm −2 , comparable to sulfide electrolytes but with higher oxidation stability. Additionally, Li 6 PI 3 enables stable cycling of Li//Li cells with Li 3 LuCl 6 electrolytes at 0.5 mA cm −2 for 400 cycles and maintains 86.5% capacity in Li//LiCoO 2 cells after 220 cycles at 30 °C, paving the way for high‐performance ASSLMBs.

Chemistry

Competitive Sorption of H 2 O and CO 2 in Clay Mineral Interlayers

The first-reported competitive CO 2 –H 2 O sorption isotherms on a naturally occurring expandable clay mineral (saponite) exchanged with Na, K, and Cs at near ambient CO 2 concentrations (1% CO 2 ) are reported by combining ATR-FTIR spectroscopy with gravimetric sorption methods. Little CO 2 sorption was observed at high relative humidity (RH) but increased significantly at low RH. Unlike prior work where CO 2 sorption was reported on samples that were previously subjected to heating and/or evacuation treatment to remove sorbed H 2 O, this study manipulated CO 2 sorption by controlling RH. CO 2 sorption increased in the order Cs- > K- > Na-exchanged saponite and was anticorrelated with the Gibbs energy of hydration of the exchangeable cation. As expected, H 2 O sorption followed the opposite trend, with increased H 2 O sorption occurring in the order Na > K > Cs. The amount of CO 2 sorbed using 1 atm CO 2 (p/p o = 1.0) ranged from 50 to 30 mg CO 2 /g clay and from 1.25 to 0.8 mg CO2 /g clay for 1% CO 2 (p/p o = 0.01) in N 2 . The sensitivity of the ATR-FTIR measurements is demonstrated by detecting the CO 2 stretch of adsorbed CO 2 from air containing 500 ppmv CO 2 . The spectral features of sorbed CO 2 were minimally affected by the nature of the exchangeable cation or variations in H 2 O content. However, the position of the HOH bending band shifted significantly from 1638 to 1610 cm –1 as H 2 O content decreased, reflecting changes in intermolecular hydrogen bonding between H 2 O molecules in the saponite interlayer. The shift in position of the HOH bending band to lower energy was coincident with increased CO 2 sorption. CO 2 sorption in clay mineral interlayers is consistent with sorption on weakly hydrated partially hydrophobic sites found on low charge density smectites and is enhanced by lower RH and by the presence of weakly hydrated exchangeable cations like Cs + or K + . In conclusion, the greatest CO 2 sorption occurs on Cs-saponite because this is the least hydrated cation of the three used in the study and indicates that CO2 sorption occurs on the neutral portion of the siloxane surface.

Johnston, Cliff T. [Purdue Univ., West Lafayette,

Hydride-Based Interlayer for Solid-State Anode-Free Battery

Solid-state batteries (SSBs) are considered a promising approach to realizing an anode-free concept with high energy densities. However, the initial Coulombic efficiency (ICE) has remained insufficient for anode-free batteries using sulfide-based solid electrolytes (SEs). Herein, we incorporated a hydride-based interlayer, 3LiBH 4 -LiI (LBHI), between a typical sulfide SE, Li 6 PS 5 Cl, and the Cu current collector. Further, by investigating the Li plating and stripping behaviors and the (electro)chemical stability between SEs and plated Li, we demonstrated that LBHI can effectively improve interfacial stability, leading to an ICE exceeding 94% in anode-free half cells. This interlayer also improves Coulombic efficiencies and specific capacities in anode-free full cells. Furthermore, the utilization of LBHI enables one to study Li plating behaviors without interference from interfacial (electro)chemical instabilities. The analysis of stack pressure evolution during electrochemical cycling reveals that soft shorting in SSBs arises from both dendrite formation and deformation, offering insights into further optimizing solid-state anode-free batteries.

25 ENERGY STORAGE

Ag Intercalation in Layered Cs 3 Bi 2 Br 9 Perovskite for Enhanced Light Emission with Bound Interlayer Excitons

Cesium bismuth bromide (CBB) has garnered considerable attention as a vacancy-ordered layered perovskite with notable optoelectronic applications. However, its use as a light source has been limited due to its weak photoluminescence (PL). Here, we demonstrate metal intercalation as a novel approach to engineer the room-temperature PL of CBB using experimental and computational methods. Ag, when introduced into CBB, occupies vacant sites in the spacer region, forming octahedral coordination with surrounding Br anions. First-principles density functional theory calculations reveal that intercalated Ag represents the most energetically stable Ag species compared to other potential forms, such as Ag substituting Bi. The intercalated Ag forms a strong polaronic trap state close to the conduction band minimum and quickly captures photoexcited electrons with holes remaining in CBB layers, leading to the formation of a bound interlayer exciton, or BIE. The radiative recombination of this BIE exhibits bright room-temperature PL at 600 nm and a decay time of 38.6 ns, 35 times greater than that of free excitons, originating from the spatial separation of photocarriers by half a unit cell separation distance. The BIE as a new form of interlayer exciton is expected to inspire new research directions for vacancy-ordered perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Controlling Interlayer Disorder Toward Reversible Phase Transition in a Layered Sodium Manganese Oxide Cathode

Sodium manganese oxides are promising Na-ion battery cathodes but they suffer from irreversible phase transitions during electrochemical reactions. Most strategies to date have aimed to suppress the phase transitions by stabilizing their layered structures through limiting the content of extractable Na + . Here, we conversely increase atomic disorder in the Na-birnessite, a layered sodium manganese oxide, and thereby modulate its phase transition behavior toward improved electrochemical reversibility. Our study reveals that Mn vacancies and Mn migrated into the interlayer affect interlayer local environment of Na + and water molecules consequently enhancing Na + mobility. We observe better capacity retention for disordered “D-Na-birnessite”, which undergoes a reversible phase transition from the birnessite-type structure to an O′3-type α-Na x MnO 2 -like structure through another intermediate metastable birnessite-type phase. In conclusion, this research highlights the positive effects of atomic disorder to regulate phase transition routes for achieving superior electrochemical reversibility, finally paving the way to overcoming the limits of layered oxide cathodes.

Kang, Seongkoo [Korea Univ., Seoul, (Korea, Republ