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.

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Two sets of alloys, Mg-Zn-Ca-xNi (0 ≤ x ≤ 5), have been developed with tunable corrosion and mechanical properties, optimized for fracturing materials. High-zinc artificial aged (T6) Mg-12Zn-0.5Ca-xNi (0 ≤ x ≤ 5) series, featuring a straightforward preparation method and the potential for manufacturing large-scale components, exhibit notable corrosion rates up to 29 mg cm⁻² h⁻¹ at 25 °C and 643 mg cm⁻² h⁻¹ at 93 °C. The high corrosion rate is primary due to the Ni–containing second phases, which intensify the galvanic corrosion that overwhelms their corrosion barrier effect. Low-zinc rolled Mg-1.5Zn-0.2Ca-xNi (0 ≤ x ≤ 5) series, characterizing excellent deformability with an elongation to failure of ∼26 %, present accelerated corrosion rates up to 34 mg cm⁻² h⁻¹ at 25 °C and 942 mg cm⁻² h⁻¹ at 93 °C. The elimination of corrosion barrier effect via deformation contributes to the further increase of corrosion rate compared to the T6 series. Additionally, Mg-Zn-Ca-xNi (0 ≤ x ≤ 5) alloys exhibit tunable ultimate tensile strengths ranging from ∼190 to ∼237 MPa, depending on their specific composition. The adjustable corrosion rate and mechanical properties render the Mg-Zn-Ca-xNi (0 ≤ x ≤ 5) alloys suitable for fracturing materials.

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Rolled Mg-Al-Sn series alloys generally possess limited formability due to the formation of strong basal texture. Texture weakening is an effective way to enhance formability, but usually accompanied with decreasing strength. In this work, synergistic enhancement of strength and formability is achieved in a Mg-3Al-1Sn-0.5Ca-0.1Sm (ATXS3110) alloy by 0.2 wt.% Mn addition combined with high temperature rolling, exhibiting a high index Erichsen (I.E.) value of ∼8.1 mm and near-isotropic mechanical properties. On one hand, after Mn addition, the grain refinement from ∼7.6 µm to ∼4.1 µm results in suppression of extension twinning, thereby preventing the development of strong basal texture upon stretch forming. On the other hand, trace Mn addition narrows the grain size distribution and promotes the formation of uniform fine grains, which induces homogeneous deformation during stretch forming. Moreover, grain refinement and high-density nano-sized precipitates caused by trace Mn addition increase the strength. This work may provide insights into designing low-cost Mg-Al-Sn series alloys with superior comprehensive mechanical properties for further structural applications.

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Additively manufactured Nitinol (NiTi) architectured materials, designed with unit cell architectures, hold promise for customisable applications. However, the common assumption of homogeneity in modeling and additive manufacturing of these architectured materials needs further investigation because geometric-dependent melt pool behaviour results in inhomogeneous microstructure and thermomechanical properties. This study shows that property inhomogeneity at the mesoscale is one reason for pseudo-linear response and partial superelasticity of the fabricated NiTi body-centered cubic (BCC) architectured materials. We modeled using a phenomenological constitutive relation and additively manufactured NiTi architectured materials with varying relative densities. These fabricated samples showed distinct microstructural textures and compositions that affected their local recoverability. The edge effects and laser turn regions were identified as the causes underlying the observed microstructural inhomogeneity. The dimensionless Fourier number is used to describe the transition of printing modes. This study provides valuable information on rigorous experimental/computational consistency in future work.

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Boron doped MoSi₂ particles have been envisioned as sacrificial particles for self-healing thermal barrier coatings (TBCs) but their oxidation behaviour is yet not well understood. In this work, oxidation of MoSi₂ based particle is studied in the temperature range of 1050–1200 °C. The oxidation proceeds from a transient to a steady-state oxidation stage. The kinetics during steady-state oxidation is captured with a thermal diffusion-based model. As compared to the oxidation of pure MoSi₂ particles, the addition of boron strongly enhances the silica formation. Also, a finer dispersion of MoB_x in the MoSi₂ matrix accelerates the formation of silica. The oxide growth rate constant increases proportional with the boron content of the MoSi₂ particles. This enhanced oxidation is related to the microstructure of the oxide scale. Upon oxidation, boron yields B₂O₃, which promptly merge with SiO₂ to form amorphous borosilicate, hindering the formation of crystalline SiO₂. Consequently, the migration of oxygen in the borosilicate oxide scale is faster than in the silica oxide scale on pure MoSi₂ particles.

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This study investigated the feasibility of in-situ manufacturing of a functionally graded metallic-regolith multimaterial. To fabricate the gradient, digital light processing, an additive manufacturing technique, and spark plasma sintering were selected due to their compatibility with metallic-ceramic processing in a space environment. The chosen methods were initially assessed for their ability to effectively consolidate regolith alone, before progressing to sintering regolith directly onto metallic substrates. Optimised processing conditions based on the initial powder particle size, different compositions of the lunar regolith powders and sintering temperatures were identified. Experiments have successfully proven the consolidation of lunar regolith simulants first via near-net shaping with digital light processing and then spark plasma sintering at 1050 ℃ under 80 MPa. The metallic powders were fully densified at relatively low temperatures and a pressure of 50 MPa with spark plasma sintering. Furthermore, the lunar regolith and Ti6Al4V gradient were found to be the most promising multimaterial combination. While the current study showed that it is feasible to manufacture a functionally graded metallic-regolith, further developments of a fully optimised method have the potential to produce tailored, high-performance multimaterials in an off-earth manufacturing setting for the production of aerospace, robotic, or architectural components.@en

Shape memory alloys (SMAs), such as nickel-titanium (NiTi) alloys or Nitinol, possess remarkable properties, including superelasticity and shape memory effects, which are attributed to the reversible martensitic transformation. However, traditional manufacturing of NiTi SMAs is challenging due to its high ductility and reactivity, which limits NiTi applications to simple geometries. In this context, laser powder bed fusion (L-PBF), an additive manufacturing technique, emerges as a promising solution capable of overcoming these limitations and introducing the concept of four-dimensional (4D) printing. This approach enables the creation of morphing shapes that can be activated by external stimuli, such as heat or stress, particularly beneficial for SMAs.@en

The pursuit of enhancing NiTi superelasticity through laser powder bed fusion (L-PBF) and [001] texture creation poses a challenge due to increased susceptibility to hot cracking in the resulting microstructure with columnar grains. This limitation restricts NiTi's application and contributes to material waste. To overcome this, we introduce a pioneering approach: utilising spark plasma sintering (SPS) to heal directional cracks in [001] textured L-PBF NiTi shape memory alloy. Diffusion bonding and oxygen utilisation for Ti₂NiO_x formation was found to successfully heal the cracks. SPS enhances mechanical properties, superelasticity at higher temperatures, and two-way shape memory strain during thermomechanical cycling. This work provides an alternative solution for healing cracks in L-PBF parts, enabling the sustainable reuse of cracked materials. By implementing SPS, this approach effectively addresses hot cracking limitations, expanding the application potential of L-PBF NiTi parts while improving their functional and mechanical properties.

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Superelastic metallic materials possessing large recoverable strains are widely used in automotive, aerospace and energy conversion industries. Superelastic materials working at high temperatures and with a wide temperature range are increasingly required for demanding applications. Until recently, high-temperature superelasticity has only been achievable with multicomponent alloys fabricated by complex processes. In this study, a novel framework of multi-scale models enabling texture and microstructure design is proposed for high-performance NiTi fabrication via laser powder bed fusion. Based on the developed framework, a Ni-lean Ni(49.4 at.%)-Ti alloy is, for the first time, endowed with a 4% high-temperature compressive superelasticity. A 001 texture, unfavorable for plastic slip, is created to realize enhanced functionality. The unprecedented superelasticity can be maintained up to 453 K, which is comparable with but has a wider superelastic temperature range (∼110 K) than rare earth alloyed NiTi alloys, previously only realizable with grain refinement, and other complicated post-processing operations. At the same time, its shape memory stability is also improved due to existing textured 100 martensite and intergranular precipitation of Ti₂NiOx. This discovery reframes the way that we design superior performance NiTi based alloys through directly tailoring crystallographic orientations during additive manufacturing.

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To prevent premature triggering of the healing reaction in Mo-Si containing self-healing thermal barrier coating system, an oxygen impenetrable shell (α-Al₂O₃) around the sacrificial healing particles (MoSi₂) is desired. Here an encapsulation method is presented through selective oxidation of Al in Mo(Al_xSi_1-x)₂ particles. Healing particles of Mo(Al_xSi_1-x)₂ is designed in terms of alumina shell thickness, particle size and fraction Al dissolved. By replacing Si by Al in MoSi₂ up to the maximum solubility (x = 0.65) a strong crack healing ability is maintained (relative volume expansion ≥ 40 %). The formed exclusive α-Al₂O₃, featuring a two-layered structure, results from a counter-diffusion process along the grain boundaries, and its oxidation kinetics fits well with the 3D diffusion-Jander model. After 16 h exposure in gaseous ambient with a pO₂ of 5 × 10^-10 atm. at 1100 °C, a closed and dense shell of α-Al₂O₃ is formed with a thickness of about 1.3 µm. The oxide shell produced under this condition provided healing particles with significantly improved stability upon exposure to high pO₂ of 0.2 atm. at 1100 °C for 50 h. The particles after exposure feature an inner core of MoSi₂ with Al completely consumed and an oxide shell of α-Al₂O₃.

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Electrochemical tests and surface analysis measurements were performed to study the corrosion behavior in a 0.9 wt.% NaCl solution at 37 °C of three NiTi shape memory alloys fabricated by laser-powder bed fusion (L-PBF). The passive film characteristics and corrosion resistance of L-PBF NiTi showed different features as a function of their preparation process settings. The passivation rate for L-PBF NiTi surfaces including defects, such as keyhole pores and cracks which showed high electrochemical activity accelerating the passivation reaction process, was higher in the early stages of immersion, but the corrosion resistance provided by such a rapidly formed passive film containing higher defect density is lower than that for an initially defect-free surface. The thickness of the passive film including a higher defect density does not necessarily relate to the corrosion resistance. The L-PBF NiTi prepared at a linear energy density of 0.2 J/m and volumetric energy density of 56 J/mm³ shows the least defects. Also, an outer Ti-rich and inner Ni-rich dense and corrosion protective passive film could be obtained for these L-PBF NiTi samples, which also results in a relatively low Ni ion release rate. A passive film model based on thickness, composition and defect density properties as a function of processing conditions is proposed to explain the difference in corrosion resistance of the various L-PBF NiTi.

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Electrochemical tests and surface analysis were applied to study the corrosion behavior and passive film characteristics of three-dimensional-printed NiTi shape memory alloys fabricated by laser-powder bed fusion (L-PBF) in artificial saliva at 37 °C. The passivity of L-PBF NiTi shows to be influenced by the process parameters and resulting morphological and physicochemical surface properties. The results show that the defects at the surface of L-PBF NiTi can promote the passivation rate in the early stages of exposure but a slowly formed passive film shows the best corrosion protection. The thickness of the passive film is positively correlated with its corrosion protective performance. The L-PBF NiTi alloy prepared at a linear energy density of 0.2 J·m⁻¹ and volumetric energy density of 56 J·mm⁻³ shows the least defects and best corrosion protection. An outer Ti-rich and inner Ni-rich dense passive film could be also obtained showing higher corrosion resistance. Graphic Abstract: [Figure not available: see fulltext.]

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In energy absorption applications, architectured metallic materials generally suffer from unrecoverable deformation as a result of local yield damage or inelastic buckling. Nitinol (NiTi) offers recoverable deformation and energy dissipation due to its unique superelasticity, which can change the way we design and additively manufacture energy-absorbing architectured materials. The interplay between microstructure, mesoscopic deformation, and macroscopic thermomechanical response of NiTi architectured materials is still not studied in depth. In this work, NiTi architectured materials featuring anisotropic superelastic response, recoverable energy absorption and damping were successfully modeled and manufactured using laser powder bed fusion (L-PBF). Extensive numerical models demonstrated that NiTi architectured materials exhibit temperature-dependent superelasticity and effective transformation stress which can be controlled by the relative density and cell architecture. An effective transformation surface was developed based on the extended Hill's model, illustrating anisotropy is temperature-independent. Stable cyclic behavior with 2.8 % of reversible strain and damping behavior was successfully achieved in cyclic compressive tests without yielding damage or plastic buckling, which further illustrates that the progressive martensitic transformation is the main deformation and energy dissipation mechanism. A comparative study between designed herein body centered cubic (BCC) and octet structures showed that local microstructures significantly affect the deformation modes. The integrated computational and experimental study enables tailoring the superelasticity by combining structural design and microstructural control. Architectured materials designed in this study are potentially applicable as reusable impact absorbers in aerospace, automotive, maritime and vibration-proof structures.

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Boron containing MoSi₂ is a promising material for applications at high temperature, but the oxidation mechanism is still unclear. In this work, the high temperature (1100 °C) oxidation of B doped MoSi₂ in synthetic air has been investigated. A (boro)silicate layer is formed on the surface of the alloy, which features a mixture of amorphous SiO₂ and cristobalite. After an initial transient period, the oxidation kinetics follows a parabolic growth rate law. The growth rate constant of the oxide layer is enhanced by the boron in the alloy by 90 % per at.% B. The increase in growth rate is associated with boron mitigating the formation of cristobalite thereby promoting the formation of amorphous SiO₂.

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Additive manufacturing of NiTi shape memory alloys has attracted attention in recent years, due to design flexibility and feasibility to achieve four-dimensional (4D) function response. To obtain customized 4D functional responses in NiTi structures, tailorable phase transformation temperatures and stress windows as well as one-way or two-way shape memory properties are required. To achieve this goal, various heat treatments, including direct aging, annealing and annealing followed by aging, were optimized for the Ti-rich NiTi (Ni49.6Ti (at. %)) fabricated by laser powder bed fusion (L-PBF). Microstructural evolution, phase transformation, precipitation and shape memory behaviour were systematically investigated by multiscale correlative microstructural, differential scanning calorimetry analysis and thermomechanical analysis. Based on optimized heat treatments, ∼25 K phase transformation temperature windows and ∼90 MPa stress windows were achieved for the one-way shape memory effect. Solutionized annealing was found to be the most effective way to improve one-way shape memory degradation resistance, due to the reduction of defects and solid solution strengthening. One of the main findings of this study is that the heterogonous microstructures between hard intergranular Ti₂NiO_x and soft NiTi matrix, induced by solutionized annealing with subsequent aging, result in strain partitioning and enclosing the internal stress state, which was found to promote a pronounced two-way shape memory effect response. The results of this work provide in-depth knowledge on tailoring and designing functional shape memory characteristics via heat treatments, which contributes to expanding L-PBF NiTi application fields, such as biomedical implants, aerospace components, and other advanced engineering applications.

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Laser powder bed fusion (L-PBF), categorized as additive manufacturing technique, has a capability to fabricate NiTi (Nitinol) shape memory alloys with tailorable functional properties and complex geometries. An important processing parameter, hatch distance (h), is often related to macroscale structural defects; however, its role on controlling the microstructure and functional properties is usually underestimated in L-PBF of NiTi. In this work, equiatomic NiTi (50.0 at% Ni) parts were fabricated with various hatch distances to tailor the microstructure and their shape memory characteristics. Contrary to what is observed in Ni-rich NiTi alloys, in this work, we demonstrate that phase transformation temperatures of L-PBF equiatomic NiTi do not decrease proportionally with hatch distance but rather relate to a critical hatch distance value. This critical value (120 μm) is derived from the synergistic effect of thermal stress and in situ reheating. Below this value, epitaxial grain growth and in situ recrystallization are enhanced, while above, irregular grains are formed and dislocations induced by thermal stresses decrease. However, the critical value found herein is characterized by high dislocation density and fine grain size, resulting in a superior thermal cyclic stability. The proposed finite element model is proven to be an effective tool to understand and predict the effect of hatch distance on grain morphology and dislocation density evolutions in L-PBF NiTi SMAs. In the present study, we provide a comprehensive understanding for in situ controlling L-PBF NiTi microstructure and functional characteristics, which contributes to designing 4-dimensional shape memory alloys.

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Nitinol (NiTi) shape memory alloys fabricated by Laser Powder Bed Fusion (L-PBF) Additive Manufacturing (AM) have attracted much attention in recent years, as compared with conventional manufacturing processes it allows to produce Nitinol parts with high design complexity. Avoidance of defects during L-PBF is crucial for the production of high quality Nitinol parts. In this study, analytical models predicting melt pool dimensions and defect formation criteria were synergistically used to develop processing maps demonstrating boundary conditions for the formation of such defects, as balling, keyhole-induced pores, and lack of fusion. Experimental validation has demonstrated that this method can provide an accurate estimation and guide manufacturability of defect-free Nitinol alloys. Moreover, the crack formation phenomena were experimentally analysed, which showed that a low linear energy density (E_l) should be chosen to avoid cracks in the optimized process windows. Based on model predictions and experimental calibrations, Nitinol samples with a relative density of more than 99% were successfully fabricated.

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Additively manufactured (AM) biodegradable magnesium (Mg) scaffolds with precisely controlled and fully interconnected porous structures offer unprecedented potential as temporary bone substitutes and for bone regeneration in critical-sized bone defects. However, current attempts to apply AM techniques, mainly powder bed fusion AM, for the preparation of Mg scaffolds, have encountered some crucial difficulties related to safety in AM operations and severe oxidation during AM processes. To avoid these difficulties, extrusion-based 3D printing has been recently developed to prepare porous Mg scaffolds with highly interconnected structures. However, limited bioactivity and a too high rate of biodegradation remain the major challenges that need to be addressed. Here, we present a new generation of extrusion-based 3D printed porous Mg scaffolds that are coated with MgF2 and MgF2-CaP to improve their corrosion resistance and biocompatibility, thereby bringing the AM scaffolds closer to meeting the clinical requirements for bone substitutes. The mechanical properties, in vitro biodegradation behavior, electrochemical response, and biocompatibility of the 3D printed Mg scaffolds with a macroporosity of 55% and a strut density of 92% were evaluated. Furthermore, comparisons were made between the bare scaffolds and the scaffolds with coatings. The coating not only covered the struts but also infiltrated the struts through micropores, resulting in decreases in both macro- and micro-porosity. The bare Mg scaffolds exhibited poor corrosion resistance due to the highly interconnected porous structure, while the MgF2-CaP coatings remarkably improved the corrosion resistance, lowering the biodegradation rate of the scaffolds down to 0.2 mm y-1. The compressive mechanical properties of the bare and coated Mg scaffolds before and during in vitro immersion tests for up to 7 days were both in the range of the values reported for the trabecular bone. Moreover, direct culture of MC3T3-E1 preosteoblasts on the coated Mg scaffolds confirmed their good biocompatibility. Overall, this study clearly demonstrated the great potential of MgF2-CaP coated porous Mg prepared by extrusion-based 3D printing for further development as a bone substitute. This journal is

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Thermal conductivity is a key parameter for high performance material needed for electronic devices. While most commercially used Mg foundry alloys exhibit low thermal conductivities. In this work, we developed an Mg–3RE–0.5Zn alloy that is suitable for high pressure die cast (HPDC) ultrathin wall cellphone components. The thermal conductivity of this alloy was measured to be 133.9 W/(m·K) at room temperature, approximately 85% that of pure Mg (156 W/(m·K)). Meanwhile, it exhibited acceptable room-temperature mechanical properties with high yield strength of ∼153 MPa, ultimate tensile strength of ∼195 MPa, and elongation of ∼4.3%. The excellent combination of superior thermal conductivity and high strength is attributed to low solute atoms in the α-Mg matrix and the formation of networked (Mg, Zn)₁₂RE eutectic phase. The results from this study will be helpful for developing new HPDC Mg alloys with more excellent performances and promoting the wider application of Mg alloys.

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