Zirconium carbide (ZrC) is a candidate material for extreme environments due to its exceptional thermal and mechanical properties. However, its oxidation behavior, particularly the formation of the Zr–C–O layer, requires further clarification. In this study, we investigated the oxidation of spark plasma sintered ZrC under varying temperatures and oxygen partial pressures, revealing a double-layer oxide scale. At the interface between ZrC and the Zr–C–O layer, we identified previously unreported oxidation front stripes composed of cubic zirconia, along which elliptical submicropores formed, suggesting preferential CO₂ release pathways. The Zr–C–O layer itself was significantly enriched with amorphous free carbon. Based on these findings, we developed a phenomenological model that incorporated the formation of the compact Zr–C–O layer to predict oxide scale growth. This multiscale approach provides new insights into ZrC oxidation mechanisms and supports the design of oxidation-resistant ceramics for aerospace and nuclear applications.

Zirconium diboride (ZrB₂)–silicon carbide (SiC) composites are promising candidates for ultra-high temperature applications, yet optimizing their densification and mechanical performance without sintering additives remains a challenge. This study systematically investigates the independent and combined effects of three critical spark plasma sintering (SPS) parameters, that is, temperature, applied pressure, and dwell time, on the densification behavior, microstructure, and mechanical properties of ZrB₂–20 vol% SiC composites. Building upon prior work on powder preparation effects (e.g., Tungsten Carbide (WC) vs. ZrO₂ milling), this research uniquely focuses on how precise control of sintering conditions alone can tailor final material characteristics. The results demonstrate that optimizing sintering parameters yields significant property enhancement, achieving a maximum relative density of 99.2% (at 2100°C, 65 MPa, 15 min) and peak flexural strength of 516 MPa (at 2000°C, 65 MPa, 60 min). Hardness and fracture toughness reached 17.08 GPa and 3.85 MPa m^1/2, respectively, under optimized conditions. Through detailed microstructural and performance analysis, this work explains the fundamental role of individual sintering parameters in governing densification kinetics and mechanical outcomes. The findings offer practical guidance for additive-free, energy-efficient processing of ZrB₂–SiC ceramics for advanced aerospace and thermal protection systems.

ZrC Ultra-High Temperature Ceramic is a promising material for future extreme environment applications. However, its susceptibility to oxidation at elevated temperatures poses a significant challenge. There remains unresolved controversy in literature regarding its oxidation kinetics and activation energies. The temperature, oxygen pressure and time effects on the oxidation and passivation of ZrC are still not fully understood. To address these questions, we fabricated near-stoichiometric ZrC ceramic via spark plasma sintering (SPS) and for the first time investigated the temperature-oxygen pressure-time (T-P-t) dependent oxidation kinetics of SPS-sintered ZrC. A three-stage oxidation mechanism including a passivation stage was reported. The study also revealed the complexity of activation energy dependence on temperature and pressure within the 3D T-P-t space. Additionally, it uncovered the conditions necessary to maintain the passivation of ZrC. These findings provide valuable insights for future design of oxidation-resistant ZrC and carbides, paving the way for advancements in materials for extremes.

Liquid metal embrittlement (LME) during resistance spot welding (RSW) of twinning induced plasticity (TWIP) steel is primarily driven by stress-assisted grain boundary (GB) diffusion of zinc (Zn). Although GB diffusion is widely recognized as the dominant LME mechanism, experimental quantification is challenging due to resolution limitations. This study characterizes Zn diffusion in TWIP steel during RSW by conducting energy dispersive X-ray spectroscopy (EDS) line scans ahead of LME cracks in both the rolling direction (RD) and normal direction (ND) over weld times from 700 to 1700 ms. Results reveal that Zn diffusion distance increases with weld time, with consistently higher diffusion in the ND. To compare experimental measurements with diffusion theory, an FEA simulation based on Fick’s law was employed to approximate bulk Zn diffusion under varying temperatures. The model predicts Zn diffusion trends consistent with experimental observations. Although the diffusion distance predicted in the simulation exceeds measured values, directional trends are accurately captured. A theoretical framework to compare GB and bulk diffusion was proposed. GB diffusion distance of Zn is estimated to be approximately 30 times greater than bulk diffusion, establishing a quantitative link between weld time and Zn diffusion during RSW of TWIP steel.

Cemented carbides are essential in applications requiring exceptional hardness and wear resistance. However, the reliance on cobalt as a binder raises concerns related to cost, supply security, and health. High-entropy alloys (HEAs) are promising cobalt-free binders offering favorable mechanical properties and potential grain-growth control. This work presents a new approach for the development of Co-free WC-based cemented carbide employing an HEA binder designed through CALPHAD-guided simulations. An optimized composition corresponding to Al5Cr5Cu10Fe35Mn10Ni35 (at%) alloy is predicted to be FCC-dominant with minimal σ-phase formation and good compatibility with WC. A preliminary batch of powder of the proposed binder was produced by blending elemental powders, arc remelting, and ultrasonic atomization, yielding predominantly spherical particles with a dendritic microstructure. WC–HEA composites (WC–12 wt% HEA) were then prepared by ball milling, pressing, vacuum sintering, and sinter-HIP for a first evaluation of the microstructure and achievable hardness. The microstructure exhibited residual porosity without significant WC grain coarsening. XRD analyses showed the dominant presence of WC, along with FCC and M3W3C phases (M mainly Fe and Mn), indicating thermal interaction between the binder and WC. Despite these effects, the composite achieved a hardness of 1913 HV and retained a fine WC grain size (0.86 μm). The proposed design approach allowed the definition of a promising Co-free binder composition based on HEA with the expected microstructure, which will need further evaluation, especially aimed at investigating toughness properties as a function of the WC content.

This study concentrates on the fatigue crack propagation behaviour of a high-strength low-alloy (HSLA) steel and austenitic stainless (AS) steel bi-material part, as obtained by wire arc additive manufacturing (WAAM). Due to partial mixing in the weld pool, the first layer of AS steel laid onto the previously deposited HSLA steel results in a diluted interface layer of distinct chemical and microstructural characteristics. Average Paris parameters are obtained for the interface layer along transverse and longitudinal planes to the deposition direction (BD-LD plane: m = 2.79, log₁₀(C) = –7.83 log₁₀(da/dN)) (BD-TD plane: m = 3.47, log₁₀(C) = –8.39 log₁₀(da/dN)). However, it is observed that this interface layer manifests an intriguing crack propagation behaviour. FCGR consistently drop as the crack front transitions from undiluted AS steel to the interface. At ΔK = 20 MPa⋅m^0.5, the greatest Δ is −0.77 log₁₀ steps (R = 0.1). As cracks near the HSLA fusion line, rates re-accelerate up to + 0.75 log₁₀ steps (R = 0.5). The phenomenon is attributed to the interplay between deformation-induced martensitic transformation and pre-existing allotropic martensite. Our findings, derived from a series of fatigue tests in correlation with multiscale microstructural and fracture characterization, offer insights into the damage-tolerant behaviour of these bi-material structures.

NiTi alloys, widely used for their shape memory and superelastic properties, face corrosion challenges when fabricated via laser powder bed fusion (LPBF). This study investigates the dual-phase formation in LPBF NiTi and its impact on corrosion resistance. Thermal simulations and microstructural analysis reveal that thermal stress drives martensite formation near melt pool boundaries. Martensitic regions act as anodic sites, leading to localized corrosion. Optimizing LPBF parameters produced single-phase [001]-textured NiTi, eliminating martensite and significantly reducing the corrosion current by almost two orders of magnitude and enhancing superelastic performance simultaneously. These findings highlight texture control as a key strategy to improve corrosion resistance and functionality for advanced applications.

Copper-steel functionally graded materials combine the thermal conductivity of copper with the mechanical strength of steel. This study examines the microstructural, mechanical, and thermophysical properties of the constitutive layers of copper-4130 steel functionally graded material fabricated via laser directed energy deposition, considering four intermediate compositions: 100% 4130, 75% 4130 – 25% Cu, 50% 4130 – 50% Cu, and 25% 4130 – 75% Cu. It was observed that the amount of Cu-rich terminal liquid governs crack formation and backfilling during solidification, while Cu-Fe liquid phase separation and Marangoni convection within the melt pool generate macrostructures composed of alternating Cu- and Fe-rich phases. Increasing Cu content progressively enhances thermal diffusivity due to the formation of interconnected copper regions. The application of quenching and tempering treatments induced softening of Cu-containing samples due to Cu recrystallization and diffusion from supersaturated Fe-rich phases. Although solidification cracking was only observed in 75% 4130–25% individual samples, the analysis of a complete multilayer structure revealed that interlayer mixing causes local compositional variations, extending cracking susceptibility beyond this region. These findings provide insights into the key factors governing laser directed energy deposition of copper-steel functionally graded materials, supporting process optimization and predictive model development to enhance manufacturability.

The sensitivity of the single-phase, low thermal expansion (LTE) alloy 36 (Fe-36Ni) to intergranular cracking hinders its processability during additive manufacturing. This study investigates the effect of accelerated cooling via a CO₂ jet and the addition of TiC particles on the cracking susceptibility of the LTE36 alloy during wire-arc additive manufacturing (WAAM). Results show that accelerated cooling reduces inter-pass deposition times and the susceptibility to cracking due to increased heat dissipation. A crack-free microstructure was achieved only with the addition of TiC particles, which pinned the high-angle grain boundaries and induced tortuosity, thereby limiting grain growth and mitigating intergranular cracking. Mechanical performance was restored compared to the cracked condition, and the critical LTE property of the as-deposited LTE36 alloy was improved due to the enhanced ferromagnetic character of the alloy. Therefore, the combined approach effectively mitigated intergranular cracking while retaining the LTE behaviour during WAAM of the LTE36 alloy.

Improving the reliability of advanced high-strength steels (AHSS) for automotive applications requires a thorough understanding of liquid metal embrittlement (LME) crack propagation micromechanisms. This study investigates how microstructural features govern crack propagation paths in Zn-galvanised twinning-induced plasticty steel. LME was induced via Gleeble hot tensile tests at 800 °C, and a correlative analysis of the fracture surface's transversal plane revealed key crack-microstructure interactions. The results show that LME fracture is predominantly intergranular, preferentially occurring along high-angle, high-energy random grain boundaries (40°–56°). To quantify the effect of tensile stress on grain boundary segments, a normalised grain boundary stress factor was defined, ranging from 0 (no tensile stress, only shear) to 1 (pure tensile stress). Generally, high-angle grain boundaries require a stress factor below 0.2 for LME, while low-angle grain boundaries (θ <15°) require at least 0.5. Most coincident site lattice boundaries between Σ5 and Σ29 are affected by LME, whereas Σ3 boundaries remain resistant, even at high stress factor. However, cases where Zn penetration was absent despite high misorientation angles and stress factors, or where cracking occurred under the lowest stress factor (parallel to the loading axis), suggest additional, unidentified factors influence LME. These findings highlight the need for advanced three-dimensional modelling to capture the complex interaction between microstructure, stress state, and Zn penetration, not fully resolved in experiments. These insights could guide the development of LME-resistant steels, supporting their safe and reliable use in the automotive industry.

This study investigates the impact of different powder milling methods on the densification and mechanical properties of ZrB₂-SiC ceramic composites processed via spark plasma sintering (SPS). Powders were prepared using two ball milling techniques: tungsten carbide (WC) and conventional ZrO₂. The densification behavior during SPS was monitored, and the sintered samples were evaluated for their relative density, hardness, fracture toughness, and flexural strength. Results show that WC milling significantly enhances densification, achieving 99.2 % relative density at 2100 °C/65 MPa/15 min, compared to 96.5 % for ZrO₂-milled samples. This improvement is due to WC's sintering aid effect, which promotes grain boundary diffusion and particle packing. However, ZrO₂-milled composites exhibit superior hardness (17.38 GPa) and fracture toughness (3.97 MPa m¹/²), attributed to their refined grain structure and the absence of softer ZrO₂ phases. Conversely, WC-milled samples show slightly higher flexural strength (384–516 MPa), likely due to the transformation toughening effect of the secondary ZrO₂ phase. Overall, WC milling improves densification and flexural strength, while ZrO₂ milling yields finer-grained composites with higher hardness and toughness, making it better suited for wear-resistant and mechanically demanding applications.

Liquid metal embrittlement (LME) presents a major barrier to the widespread adoption of advanced high-strength steels in automotive applications. Despite extensive research, decoupling its early-stage cracking and propagation micromechanisms remains challenging and is a key research gap. Distinguishing these stages is crucial to understanding the conditions and factors that are favourable for LME and to developing mitigation strategies. Moreover, it can improve the accuracy of predictive models through detailed knowledge from initiation to propagation. In this study, this challenge is addressed by performing interrupted Gleeble hot tensile tests on a Zn-galvanised twinning-induced plasticity steel, simulating resistance spot welding conditions. This approach enables tracking LME progression under applied stress and identifying fracture micromechanisms at early and advanced stages of cracking. Additionally, existing theories on LME micromechanisms are often contradictory, highlighting the need for fundamental research in this area. The findings reveal that LME begins with the contact between liquid Zn and the substrate, leading to Zn diffusion into the substrate by diffusion-induced grain boundary migration and dissolution of the substrate by erosion-corrosion. This dissolution generates defects on the substrate and facilitates Fe diffusion into liquid Zn. Subsequently, defects are filled with liquid and the Zn-rich defect tips, connected to grain boundaries, enhance Zn grain boundary diffusion and weaken intergranular cohesion. Under tensile stress, these weakened boundaries decohere and lead to crack nucleation. Newly formed crack surfaces allow fresh Fe-rich liquid Zn to penetrate, continuing the process until fracture. Future work will focus on the influence of microstructure on LME crack growth.

This work studies the hydrogen embrittlement (HE) behaviour of Dual-Phase steels with varying martensite content. Steels with martensite contents of 25 ± 5, 50 ± 4 and 78 ± 7% were realised by intercritically annealing an as-received DP steel. These steels were charged with hydrogen and consequently subjected to an in situ slow strain rate tensile test to characterise the embrittlement. It was found that the steel with 50% martensitic content showed the most ductility in air, but the highest embrittlement of 86 ± 10%. The extent of embrittlement does not increase further from the point that martensite forms a continuous network in the microstructure. The presence of martensite on the surface is linked to the formation of brittle crack initiation sites in these steels. Furthermore it was found that the anisotropic banded structure in the annealed steels promotes brittle crack propagation along the direction of banding, which originates from rolling process. This research shows that anisotropic martensite distributions as well as surface martensite should be avoided when developing rolled steels, to maximise HE resistance.

The effect of TiC and VC nano-precipitate size on the hydrogen embrittlement of ferritic steels was studied in this work. Steels containing two size distributions (10 nm or less and 10 - 100 nm) of TiC and VC carbides are subjected to tensile tests in-situ in an electrochemical hydrogen charging environment. Hydrogen is found to be trapped in interstitial matrix sites on the precipitate/matrix interface with activation energies of 14 - 20 kJ/mol and inside misfit dislocation cores with energies of 27 - 37 kJ/mol. All steels are embrittled by 15 to 20%, except the TiC steel with semi-coherent carbides up to 100 nm, which is embrittled by 37%. This is caused by accelerated intergranular fracture as a result of hydrogen trapped in dislocation pile-ups around grain boundary precipitates. The steel with coherent VC nano-carbides retained the highest strength and ductility during in-situ testing. This is therefore the optimal carbide configuration for use in hydrogen environments.

In this study, three-dimensional functionally graded NiTi bulk materials were fabricated using laser powder bed fusion (LPBF) by in-situ adding Ni powder into equiatomic NiTi powder. The gradient zone exhibited a Ni composition ranging from approximately 49.6 to 52.4 at.% over a distance of about 2.75 mm. The functionalities along the compositional gradient were examined through differential scanning calorimetry analysis and spherical indentation. This unique gradient resulted in location-specific functionalities, including superelasticity characterized by wide and narrow hysteresis loops, shape memory effect, and various phase transformation temperatures. The rapid cooling rate during fabrication led to the presence of excess Ni in the solid-solute state within NiTi. This unique solid-solute compositional gradient in NiTi resulted in varying lattice parameters, influencing the compatibility between martensite and austenite and allowing for tailored hysteresis. This discovery presents new avenues for designing multifunctional materials through in-situ additive manufacturing.

Microstructure features including grain morphology and texture are key factors in determining the properties of laser additively manufactured metallic components. Beyond the traditional trial-and-error approach, which is costly and time-consuming, microstructure control increasingly relies on predictions from mechanistic models. However, existing mechanistic models to predict microstructure and texture are computationally expensive. Here, we present a cellular automata solidification model, which is up to two orders-of-magnitude faster than traditional models. By analytically calculating growth length and utilizing a multi-level capture algorithm, a large time step can be employed without compromising simulation accuracy. The model is validated through simulations of 316L steel and three NiTi cases, showing good agreement with experimental results. Our findings reveal that preferential orientations are selected by the vertical and the inclined temperature gradients from multi-pass temperature profiles, leading to different microstructures and textures. Three-dimensional additive manufacturing simulations demonstrate that orientation-dependent growth patterns govern grain growth, leading to columnar, planar and spiral shaped grains. This approach offers a significant reduction in computational cost while maintaining accuracy, contributing to the practical application of microstructure control in additive manufacturing. The insights gained on grain and texture evolution pave the way for customized microstructure design through additive manufacturing.

Wire arc additive manufacturing (WAAM) offers a novel approach to fabricate functionally graded components. By changing the wire consumable between layers, chemical grading can be used to obtain specific properties across a part's volume. This is an interesting approach to design large metal components that achieve unconventional performance in demanding engineering applications, such as sulphide-resistant pressure vessels or sea ballast piping with extended lifetime. However, challenges derived from dissimilar material combinations draw the need to study the effect of compositional grading on the mechanical properties. This study focuses on the deformation and fracture toughness behaviour of WAAM-fabricated high-strength low-alloy (HSLA) and austenitic stainless (AS) steel bi-material specimens, particularly examining the diluted interface layer obtained during deposition. Tensile testing results indicate that the elastic modulus at the interface matches that of un-diluted AS steel (157 ±17 GPa) along the build direction. Fracture toughness showed a lower J_IC (180 kJ/m²) when compared to the undiluted AS steel (459 ±69 kJ/m²) and HSLA steel (408 ±25 kJ/m²). Scanning electron microscopy and electron backscatter diffraction are used to establish a connection between the microstructure at the interface and the observed mechanical properties. It is concluded that deformation at the interface is in large controlled by the deformation-induced martensitic transformation of metastable austenite. These results underline the influence of chemical dilution on the deformation mechanisms and fracture behaviour of HSLA and AS steel bi-material parts, which needs to be accounted for in the design of parts composed by this bi-metal couple.

Superelastic metamaterials have attracted significant attention recently, but achieving such functionality remains challenging due to partial superelasticity and premature fracture in additively manufactured components. To address these issues, this study investigates the premature fracture in Ni-rich NiTi metamaterials fabricated by laser powder bed fusion. A comparative analysis of two structures (Gyroid network and Diamond shell) reveals that the structural stability of bending- and stretching-dominated structures is reversed compared to typical elastic-plastic response, due to the tension-compression asymmetry of base NiTi. The premature fracture and partial superelasticity of these as-fabricated samples are attributed to low deformation ability for accommodating tensile stress. Based on these findings, a heat treatment introducing Ni₄Ti₃ precipitates was employed, successfully achieving macroscopic superelasticity in the NiTi metamaterials, with consistency between model prediction and experiments.

The effect of hydrogen charging during plastic deformation was investigated on a ferritic steel containing TiC nano-precipitates. Specimens were subjected to a slow strain rate tensile test (SSRT) up to 0, 1, or 3% plastic engineering strain, held until a total duration of 2 h to saturate with hydrogen, then fast fractured. The specimens pre-strained elastically absorbed 2.36 wppm of hydrogen, which increased to 3.69 wppm for 3% plastic strain. Only 0.72 wppm is stored in non-dislocation traps such as precipitates, grain boundaries, and lattice sites, which makes dislocations the main contributor to hydrogen trapping. The increased hydrogen uptake did not lead to a decrease in fracture strain, which remained between 6 and 10% for all pre-strains, compared to 60% for full SSRT tests that were charged for a shorter time. This research highlights the necessity of high plastic strains and the presence of hydrogen in the environment during crack growth to cause HE in ductile steels.

The binary Fe–Ni system offers alloys with notably low linear coefficients of thermal expansion (CTE), contingent upon their Ni content. In this respect twin-wire arc additive manufacturing (T-WAAM) presents the opportunity of in-situ alloying through the simultaneous feeding of two metal wires into a weld pool to obtain desired alloy compositions. This study aims to deposit a graded wall with Ni contents targeted at 42, 46, and 52 wt% in the building direction of the wall, along with a block comprising of 46 wt% Ni, employing the T-WAAM approach. The results show effective incorporation of additional Ni into the weld pool and geometrically stable weld beads in the continuous metal transfer mode during the T-WAAM process. This mode led to the defect-free and chemically stable deposition of the graded wall and the block with average Ni contents of 42.3 ± 1.1, 45.8 ± 1.4, 52.6 ± 0.8 wt%, and 46.4 ± 0.9 wt%, respectively. The measured Curie temperatures of the as-deposited alloys and the mean CTE values of alloy 46 were found to be comparable to the commercial alloys. In summary, this study validates the feasibility of in-situ deposition of low thermal expansion alloy compositions, thereby enabling the possibility of on-demand thermal expansion properties.