In Situ TEM Study of Structural Changes in Na-β″-Alumina Using Electron Beam Irradiation

Real-time structural changes in Na-β″-alumina were observed in situ using transmission electron microscopy (TEM) with electron beam irradiation. Na-β″-alumina has been widely investigated as a solid electrolyte material for sodium–sulfur secondary batteries owing to its high ionic conductivity. This high conductivity is known to be due to the Na⁺ ions on the loosely packed conduction planes of Na-β″-alumina. In the present study, we acquired real-time videos of the generation of spinel blocks caused by the conduction of Na⁺ ions. In addition, by observing Na extraction during electron beam irradiation, we experimentally confirmed that spinel block generation originates from the Na⁺ ion conduction, which has been a subject of recent debate.     

Sodium Solid Electrolytes: NaxAlOy Bilayer-System Based on Macroporous Bulk Material and Dense Thin-Film

A new preparation concept of a partially porous solid-state bilayer electrolyte (BE) for high-temperature sodium-ion batteries has been developed. The porous layer provides mechanical strength and is infiltrated with liquid and highly conductive NaAlCl₄ salt, while the dense layer prevents short circuits. Both layers consist, at least partially, of Na-β-alumina. The BEs are synthesized by a three-step procedure, including a sol-gel synthesis, the preparation of porous, calcined bulk material, and spin coating to deposit a dense layer. A detailed study is carried out to investigate the effect of polyethylene oxide (PEO) concentration on pore size and crystallization of the bulk material. The microstructure and crystallographic composition are verified for all steps via mercury intrusion, X-ray diffraction, and scanning electron microscopy. The porous bulk material exhibits an unprecedented open porosity for a Na_xAlO_y bilayer-system of ≤57% with a pore size of ≈200–300 nm and pore volume of ≤0.3 cm³∙g⁻¹. It contains high shares of crystalline α-Al₂O₃ and Na-β-alumina. The BEs are characterized by impedance spectroscopy, which proved an increase of ionic conductivity with increasing porosity and increasing Na-β-alumina phase content in the bulk material. Ion conductivity of up to 0.10 S∙cm⁻¹ at 300 °C is achieved.     

A First-Principles Study of the Cu-Containing β″ Precipitates in Al-Mg-Si-Cu Alloy

The nanostructured β″ precipitates are critical for the strength of Al-Mg-Si-(Cu) aluminum alloys. However, there are still controversial reports about the composition of Cu-containing β″ phases. In this work, first-principles calculations based on density functional theory were used to investigate the composition, mechanical properties, and electronic structure of Cu-containing β″ phases. The results predict that the Cu-containing β″ precipitates with a stoichiometry of Mg_4+xAl_2−xCuSi₄ (x = 0, 1) are energetically favorable. As the concentration of Cu atoms increases, Cu-containing β″ phases with different compositions will appear, such as Mg₄AlCu₂Si₄ and Mg₄Cu₃Si₄. The replacement order of Cu atoms in β″ phases can be summarized as one Si3/Al site → two Si3/Al sites → two Si3/Al sites and one Mg1 site. The calculated elastic constants of the considered β″ phases suggest that they are all mechanically stable, and all β″ phases are ductile. When Cu atoms replace Al atoms at Si3/Al sites in β″ phases, the values of bulk modulus (B), shear modulus (G), and Young’s modulus (E) all increase. The calculation of the phonon spectrum shows that Mg_4+xAl_2−xCuSi₄ (x = 0, 1) are also dynamically stable. The electronic structure analysis shows that the bond between the Si atom and the Cu atom has a covalent like property. The incorporation of the Cu atom enhances the electron interaction between the Mg2 and the Si3 atom so that the Mg2 atom also joins the Si network, which may be one of the reasons why Cu atoms increase the structure stability of the β″ phases.     

Calculation Based on the Formation of Mg2Si and Its Effect on the Microstructure and Properties of Al–Si Alloys

In order to investigate the effect of Mg₂Si formation on the microstructure and properties of an Al−Si alloy, the critical point of a hypereutectic Al−17Si−4Cu−Mg alloy was calculated by Pandat software. The calculation results of the equilibrium phase diagram show that the critical point for Mg₂Si phase formation for the alloy was obtained when the Mg content was 2.2%. The contents of 0.5 wt.% Mg and 2.5 wt.% Mg were selected as the research object. The content of Mg increased from 0.5 wt.% to 2.5 wt.%, the eutectic Si in the matrix was reduced, and the Chinese character-like Mg₂Si phase appeared in the microstructure. In the peak ageing state, in addition to θ″ and Q′ phases that were mainly precipitated, there was also needle-like β″ precipitation in the 2.5 wt.% Mg content alloy. Larger precipitates were found in 2.5 wt.% content alloys, mainly due to the promotion of the solid solution having the aggregation and segregation of more solute elements in the matrix. The tensile strength, elongation, and hardness of hypereutectic Al−17Si−4Cu−0.5Mg alloy under peak ageing were 331 MPa, 3.11%, and 152.1 HB, respectively. The tensile strength and the elongation decreased while the hardness increased with the 2.5 wt.% Mg content, which is due to the formation of hard and brittle Mg₂Si and Al₈FeMg₃Si, which has a splitting effect on the matrix.     

In Situ Observation of the Tensile Deformation and Fracture Behavior of Ti–5Al–5Mo–5V–1Cr–1Fe Alloy with Different Microstructures

The plastic deformation processes and fracture behavior of a Ti–5Al–5Mo–5V–1Cr–1Fe alloy with bimodal and lamellar microstructures were studied by room-temperature tensile tests with in situ scanning electron microscopy (SEM) observations. The results indicate that a bimodal microstructure has a lower strength but higher ductility than a lamellar microstructure. For the bimodal microstructure, parallel, deep slip bands (SBs) are first noticed in the primary α (α_p) phase lying at an angle of about 45° to the direction of the applied tension, while they are first observed in the coarse lath α (α_L) phase or its interface at grain boundaries (GBs) for the lamellar microstructure. The β matrix undergoes larger plastic deformation than the α_L phase in the bimodal microstructure before fracture. Microcracks are prone to nucleate at the α_p/β interface and interconnect, finally causing the fracture of the bimodal microstructure. The plastic deformation is mainly restricted to within the coarse α_L phase at GBs, which promotes the formation of microcracks and the intergranular fracture of the lamellar microstructure.     

Preparation and Properties of (YCa)(TiMn)O3?δ Ceramics Interconnect of Solid Oxide Fuel Cells

(YCa)(TiMn)O_3–δ ceramics prepared using a reaction-sintering process were investigated. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. Y₂Ti₂O₇ instead of YTiO₃ formed when a mixture of Y₂O₃ and TiO₂ with Y/Ti ratio 1/1 were sintered in air. Y₂Ti₂O₇, YTiO_2.085 and some unknown phases were detected in Y_0.6Ca_0.4Ti_0.6Mn_0.4O_3–δ. Monophasic Y_0.6Ca_0.4Ti_0.4Mn_0.6O_3–δ ceramics were obtained after 1400–1500 °C sintering. Dense Y_0.6Ca_0.4Ti_0.4Mn_0.6O_3–δ with a density 4.69 g/cm³ was observed after 1500 °C/4 h sintering. Log σ for Y_0.6Ca_0.4Ti_0.6Mn_0.4O_3–δ increased from –3.73 Scm^–1 at 350 °C to –2.14 Scm^–1 at 700 °C. Log σ for Y_0.6Ca_0.4Ti_0.4Mn_0.6O_3–δ increased from –2.1 Scm^–1 at 350 °C to –1.36 Scm^–1 at 700 °C. Increasing Mn content decreased activation energy E_a and increased electrical conductivity. Reaction-sintering process is proved to be a simple and effective method to obtain (YCa)(TiMn)O_3–δ ceramics for interconnects in solid oxide fuel cells.     

Enhanced Elevated-Temperature Strength and Creep Resistance of Dispersion-Strengthened Al-Mg-Si-Mn AA6082 Alloys through Modified Processing Route

In the present work, we investigated the possibility of introducing fine and densely distributed α-Al(MnFe)Si dispersoids into the microstructure of extruded Al-Mg-Si-Mn AA6082 alloys containing 0.5 and 1 wt % Mn through tailoring the processing route as well as their effects on room- and elevated-temperature strength and creep resistance. The results show that the fine dispersoids formed during low-temperature homogenization experienced less coarsening when subsequently extruded at 350 °C than when subjected to a more typical high-temperature extrusion at 500 °C. After aging, a significant strengthening effect was produced by β″ precipitates in all conditions studied. Fine dispersoids offered complimentary strengthening, further enhancing the room-temperature compressive yield strength by up to 72–77 MPa (≈28%) relative to the alloy with coarse dispersoids. During thermal exposure at 300 °C for 100 h, β″ precipitates transformed into undesirable β-Mg₂Si, while thermally stable dispersoids provided the predominant elevated-temperature strengthening effect. Compared to the base case with coarse dispersoids, fine and densely distributed dispersoids with the new processing route more than doubled the yield strength at 300 °C. In addition, finer dispersoids obtained by extrusion at 350 °C improved the yield strength at 300 °C by 17% compared to that at 500 °C. The creep resistance at 300 °C was greatly improved by an order of magnitude from the coarse dispersoid condition to one containing fine and densely distributed dispersoids, highlighting the high efficacy of the new processing route in enhancing the elevated-temperature properties of extruded Al-Mg-Si-Mn alloys.     

Performance Improvement of PVDF–HFP-Based Gel Polymer Electrolyte with the Dopant of Octavinyl-Polyhedral Oligomeric Silsesquioxane

Gel polymer electrolytes have the advantages of both a solid electrolyte and a liquid electrolyte. As a transitional product before which a solid electrolyte can be comprehensively used, gel polymer electrolytes are of great research value. They can reduce the risk of spontaneous combustion and explosion caused by leakage during the use of conventional liquid electrolytes. Poly(vinylidene-fluoride-co-hexafluoropropylene) (PVDF–HFP), a material with excellent performance, has been widely utilized in the preparation of gel polymer electrolytes. Here, PVDF–HFP-based gel polymer membranes with polyvinyl pyrrolidone (PVP) pores were prepared using a phase inversion method, and Octavinyl-polyhedral oligomeric silsesquioxane (OVAPOSS) was doped to improve its temperature resistance as well as its ionic conductivity, to enhance its safety and electrochemical performance. The final prepared polymer membrane had a porosity of 85.06% and still had a certain mechanical strength at 160 °C without any shrinkage. The gel polymer electrolyte prepared with this polymer membrane had an ionic conductivity of 1.62 × 10⁻³ S·cm⁻¹ at 30 °C, as well as an electrochemical window of about 5.5 V. The LiCoO₂-Li button half-cell prepared therefrom had a specific capacity of 141 mAh·g⁻¹ at a rate of 1C. The coulombic efficiency remained above 99% within 100 cycles and the capacity retention rate reached 99.5%, which reveals an excellent cycling stability.     

Microstructure and Mechanical Properties of TiN–TiB2–hBN Composites Fabricated by Reactive Hot Pressing Using TiN–B Mixture

In this study, TiN–TiB₂–hBN composite ceramics were prepared via reactive hot pressing using TiN and amorphous B powders as raw materials. Different sintering temperatures and composition ratios were studied. The results show that the 70 vol% TiN–17.6 vol% TiB₂–12.4 vol% hBN ceramic composites obtained ideal comprehensive properties at 1600 °C. The relative density, Vickers hardness, bending strength, and fracture toughness were 99%, 11 GPa, 521 MPa, and 4.22 MPa·m^1/2, respectively. Densification was promoted by the highly active reaction product TiB₂, and the structural defects formed in the grains. Meanwhile, the good interfacial bonding between TiN and TiB₂ grains and the uniform dispersion of ultrafine hBN in the matrix contributed to the excellent bending strength. Moreover, the toughening mechanism of crack deflection and grain pull-out improved the fracture toughness.     

Preparation and Characterization of High-Strength Glass-Ceramics via Ion-Exchange Method

Lithium aluminosilicate glass-ceramics (LAS GCs) are ideal shell materials for mobile phones; however, the mechanical properties of LAS GCs are comparatively lower than that of other shell materials. In this work, the impact of TiO₂/(TiO₂ + ZrO₂) ratio on properties of LAS GCs was studied and the ion-exchange methods were applied to improve the mechanical properties of LAS GCs. The results show that LAS GCs with TiO₂/(TiO₂ + ZrO₂) = 1/2 exhibit the best flexural strength (109 MPa) and Vickers hardness (525 Kg/mm²). The as-prepared glass was nucleated at 560 °C for 1 h and crystallized at 720 °C for 0.5 h. The main crystalline phases of LAS GCs are β-quartz solid solution, β-spodumene solid solution, and Li₂SiO₃. Moreover, the flexural strength and Vickers hardness of LAS GCs with TiO₂/(TiO₂ + ZrO₂) = 1/2 further increased to 356 MPa and 838 Kg/mm² after an ion-exchange at 420 °C for 6 h in pure KNO₃ molten salt. The LAS GCs with enhanced mechanical strength have the potential to be applied as mobile phone back panels.     

Impact of γ-rays Irradiation on Hybrid TiO2-SiO2 Sol-Gel Films Doped with RHODAMINE 6G

In the present paper, we investigate how the optical and structural properties, in particular the observed photoluminescence (PL) of photocurable and organic-inorganic TiO₂-SiO₂ sol-gel films doped with Rhodamine 6G (R6G) are affected by γ-rays. For this, four luminescent films, firstly polymerized with UV photons (365 nm), were submitted to different accumulated doses of 50 kGy, 200 kGy, 500 kGy and 1 MGy while one sample was kept as a reference and unirradiated. The PL, recorded under excitations at 365 nm, 442 nm and 488 nm clearly evidences that a strong signal peaking at 564 nm is still largely present in the γ-irradiated samples. In addition, M-lines and Fourier-transform infrared (FTIR) spectroscopies are used to quantify the radiation induced refractive index variation and the chemical changes, respectively. Results show that a refractive index decrease of 7 × 10⁻³ at 633 nm is achieved at a 1 MGy accumulated dose while a photo-induced polymerization occurs, related to the consumption of CH=C, Si-OH and Si-O-CH₃ groups to form Ti-O and Si-O bonds. All these results confirm that the host matrix (TiO₂-SiO₂) and R6G fluorophores successfully withstand the hard γ-ray exposure, opening the way to the use of this material for sensing applications in radiation-rich environments.     

Effect of Boron Doping on Cellular Discontinuous Precipitation for Age-Hardenable Cu–Ti Alloys

The effects of boron doping on the microstructural evolution and mechanical and electrical properties of age-hardenable Cu–4Ti (at.%) alloys are investigated. In the quenched Cu–4Ti–0.03B (at.%) alloy, elemental B (boron) is preferentially segregated at the grain boundaries of the supersaturated solid-solution phase. The aging behavior of the B-doped alloy is mostly similar to that of conventional age-hardenable Cu–Ti alloys. In the early stage of aging at 450 °C, metastable β′-Cu₄Ti with fine needle-shaped precipitates continuously form in the matrix phase. Cellular discontinuous precipitates composed of the stable β-Cu₄Ti and solid-solution laminates are then formed and grown at the grain boundaries. However, the volume fraction of the discontinuous precipitates is lower in the Cu–4Ti–0.03B alloy than the Cu–4Ti alloy, particularly in the over-aging period of 72–120 h. The suppression of the formation of discontinuous precipitates eventually results in improvement of the hardness and tensile strength. It should be noted that minor B doping of Cu–Ti alloys also effectively enhances the elongation to fracture, which should be attributed to segregation of B at the grain boundaries.     

A Study of Methylcellulose Based Polymer Electrolyte Impregnated with Potassium Ion Conducting Carrier: Impedance,EEC Modeling,FTIR, Dielectric,and Device Characteristics

In this research, a biopolymer-based electrolyte system involving methylcellulose (MC) as a host polymeric material and potassium iodide (KI) salt as the ionic source was prepared by solution cast technique. The electrolyte with the highest conductivity was used for device application of electrochemical double-layer capacitor (EDLC) with high specific capacitance. The electrical, structural, and electrochemical characteristics of the electrolyte systems were investigated using various techniques. According to electrochemical impedance spectroscopy (EIS), the bulk resistance (R_b) decreased from 3.3 × 10⁵ to 8 × 10² Ω with the increase of salt concentration from 10 wt % to 40 wt % and the ionic conductivity was found to be 1.93 ×10⁻⁵ S/cm. The dielectric analysis further verified the conductivity trends. Low-frequency regions showed high dielectric constant, ε′ and loss, ε″ values. The polymer-salt complexation between (MC) and (KI) was shown through a Fourier transformed infrared spectroscopy (FTIR) studies. The analysis of transference number measurement (TNM) supported ions were predominantly responsible for the transport process in the MC-KI electrolyte. The highest conducting sample was observed to be electrochemically constant as the potential was swept linearly up to 1.8 V using linear sweep voltammetry (LSV). The cyclic voltammetry (CV) profile reveals the absence of a redox peak, indicating the presence of a charge double-layer between the surface of activated carbon electrodes and electrolytes. The maximum specific capacitance, C_s value was obtained as 118.4 F/g at the sweep rate of 10 mV/s.     

Precipitation Hardening at Elevated Temperatures above 400 °C and Subsequent Natural Age Hardening of Commercial Al–Si–Cu Alloy

The precipitation of intermetallic phases and the associated hardening by artificial aging treatments at elevated temperatures above 400 °C were systematically investigated in the commercially available AC2B alloy with a nominal composition of Al–6Si–3Cu (mass%). The natural age hardening of the artificially aged samples at various temperatures was also examined. A slight increase in hardness (approximately 5 HV) of the AC2B alloy was observed at an elevated temperature of 480 °C. The hardness change is attributed to the precipitation of metastable phases associated with the α-Al₁₅(Fe, Mn)₃Si₂ phase containing a large amount of impurity elements (Fe and Mn). At a lower temperature of 400 °C, a slight artificial-age hardening appeared. Subsequently, the hardness decreased moderately. This phenomenon was attributed to the precipitation of stable θ-Al₂Cu and Q-Al₄Cu₂Mg₈Si₆ phases and their coarsening after a long duration. The precipitation sequence was rationalized by thermodynamic calculations for the Al–Si–Cu–Fe–Mn–Mg system. The natural age-hardening behavior significantly varied depending on the prior artificial aging temperatures ranging from 400 °C to 500 °C. The natural age-hardening was found to strongly depend on the solute contents of Cu and Si in the Al matrix. This study provides fundamental insights into controlling the strength level of commercial Al–Si–Cu cast alloys with impurity elements using the cooling process after solution treatment at elevated temperatures above 400 °C.     

Synthesis,Structural, and Mechanical Behavior of β-Ca3(PO4)2–ZrO2 Composites Induced by Elevated Thermal Treatments

Biocompatible β-Ca₃(PO₄)₂ and mechanically stable t-ZrO₂ composites are currently being combined to overcome the demerits of the individual components. A series of five composites were synthesized using an aqueous precipitation technique. Their structural and mechanical stability was examined through X-ray diffraction, Rietveld refinement, FTIR, Raman spectroscopy, high-resolution scanning electron microscopy, and nanoindentation. The characterization results confirmed the formation of β-Ca₃(PO₄)₂–t-ZrO₂ composites at 1100 °C. Heat treatment above 900 °C resulted in the degradation of the composites because of cationic interdiffusion between Ca²⁺ ions and O⁻² vacancy in Zr⁴⁺ ions. Sequential thermal treatments correspond to four different fractional phases: calcium-deficient apatite, β-Ca₃(PO₄)₂, t-ZrO₂, and m-ZrO₂. The morphological features confirm in situ synthesis, which reveals abnormal grain growth with voids caused by the upsurge in ZrO₂ content. The mechanical stability data indicate significant variation in Young’s modulus and hardness throughout the composite.     

Structure and Dielectric Behavior of Yb2O3-MgO Co-Doped 0.92BaTiO3-0.08(Na0.5Bi0.5)TiO3 Ferroelectric Relaxor

Dielectric properties and structure of 0.015Yb₂O₃-xMgO doped 0.92BaTiO₃-0.08(Na_0.5Bi_0.5)TiO₃ ceramics with x = 0.0–0.025 have been investigated. As Yb₂O₃-MgO was added into the BT-NBT, the phase changes from tetragonal to pseudo-cubic, with the tetragonality c/a decreases from 1.011 to 1.008 and XRD peaks broadened. The combined study of XRD and TEM image revealed a formation of core–shell structure in grains with core of 400–600 nm and the shell of a thickness 60–200 nm. There is a slowly phase transition against temperature from the variable temperature Raman analysis. The ferroelectric relaxor peak of BT-NBT decreases from ~4000 to ~2000 and a new broad dielectric peak with an equivalent maximum (ε_r′~2300) appears in the temperature dependent dielectric constant curve (ε_r′-T), which produces a flat ε_r′-T curve. Sample 0.92BaTiO₃-0.08(Na_0.5Bi_0.5)TiO₃-0.015Yb₂O₃-0.005 MgO and 0.92BaTiO₃-0.08(Na_0.5Bi_0.5)TiO₃-0.015Yb₂O₃-0.01MgO give a ε_r′ variation within ±14% and ±10% in 20–165 °C. The core–shell microstructure should take account for the flattened ε_r′–T behavior of these samples.     

In-Situ Study on Tensile Deformation and Fracture Mechanisms of Metastable β Titanium Alloy with Equiaxed Microstructure

Understanding the mechanisms of deformation and fracture of metastable β titanium alloys is of great significance for improving formability and service life. By combining the in-situ tensile test, TEM characterization and EBSD analysis, the tensile deformation behavior, activation of slip systems, crack initiation, and propagation of a high strength metastable β titanium alloy (Ti-5Cr-4Al-4Zr-3Mo-2W-0.8Fe) with equiaxed microstructure are investigated. The equiaxed microstructure is composed of primary α (α_p) phase, transformed β (β_t) matrix phase, and secondary α (α_s) phase. In contrast to the hexagonal α_p grain with limited slip systems, the body-centered β_t matrix has more slip systems, however the hindering effect of α_s phases on dislocation slip leads to the different deformability of the α_p phase and β_t matrix. The equiaxed α_p grains are more prone to deformation and rotation to coordinate the overall deformation. The shear band leads to the formation of sub-grain boundary and even the fragmentation of α_p grains. As a result, the microvoids tend to nucleate at the grain boundary, phase interface, slip band, and shear band. The inhomogeneous deformation in the plastic deformation zone around the crack tip is the primary cause of damage. The crack propagation caused by microvoids coalescence advances along the grain boundaries and phase interfaces in the form of intergranular, and along the activated slip systems and shear bands in the form of transgranular. Pinpointing the situation in the equiaxed microstructure and combining that in other typical microstructures will help to summarize the universal deformation and fracture mechanisms of metastable β titanium alloy, and provide a basis for alloy design and microstructure tailoring.     

Physico-Chemical Properties of NaV3O8 Prepared by Solid-State Reaction

Sodium–vanadium oxide NaV₃O₈ is synthesized via solid-state method and optimum synthesis conditions are chosen based on the data of DSC and TG analysis. The material synthesized is characterized by X-ray phase analysis, Raman spectroscopy and scanning electron microscopy. The ratio V⁴⁺/V⁵⁺ in the sample obtained is determined by X-ray photoelectron spectroscopy. Conductivity of the material synthesized was measured by impedance spectroscopy, pulse potentiometry and DC method over the range RT–570 °C. It is shown that NaV₃O₈ has rather high conductivity essentially electron in type (6.3 × 10⁻² at room temperature). AC and DC conductivity measurements are performed and cycling of symmetricNaV₃O₈|Na_3.85Zr_1.85Nb_0.15Si₃O₁₂|NaV₃O₈ cell in galvanostatic conditions. Thermal stability is studied across 25–570 °C temperature range. The results obtained are compared with the properties of NaV₃O₈ produced via aqueous solution.     

Effects of Annealing and Solution Treatments on the Microstructure and Mechanical Properties of Ti6Al4V Manufactured by Selective Laser Melting

Ti6Al4V (Ti64) alloys manufactured by selective laser melting (SLM) are well known for their susceptibility to failure at a low ductility of less than 10% due to the formation of an (α′) martensitic structure. Annealing and solution treatments as post-heat treatments of α′ are considered a good way to improve the mechanical performance of SLM-manufactured Ti64 parts. In this research, the effect of heat treatment parameters such as temperature (850 °C and 1020 °C) and cooling rate (furnace and water cooling) on the microstructure and mechanical properties of the SLM Ti64 structure was investigated. It was shown that the tensile strength/ductility of the Ti64 alloy produced by SLM was determined by the post-heat treatment. The experimental results revealed that heat treatment at 850 °C followed by furnace cooling resulted in the best possible combination of ductility (13%) and tensile strength (σ_y = 932, σ_u = 986 MPa) with a microstructure consisting mainly of 78.71% α and 21.29% β. Heat treatment at 850 °C followed by water cooling was characterized by a reduction in hardness and the formation of predominantly α plus α′′ and a small amount of β. HT850WC exhibited yield and tensile strengths of about 870 and 930 MPa, respectively, and an elongation at fracture of 10.4%. Heat treatment at 1020 °C and subsequent cooling in the furnace was characterized by the formation of an α + β lamellar microstructure. In contrast, heat treatment at 1020 °C and subsequent water cooling formed semi-equiaxial β grains of about 170 µm in diameter with longer elongated α grains and basket-weave α′. Post-treatment at 1020 °C followed by furnace cooling showed high ductility with an elongation of 14.5% but low tensile strength (σ_y = 748, σ_u = 833 MPa). In contrast, post-treatment at 1020 °C followed by water cooling showed poor ductility with elongation of 8.6% but high tensile strength (σ_y = 878, σu = 990 MPa). The effect of aging at 550 °C for 3 h and cooling in a furnace on the microstructure and mechanical properties of the specimens cooled with water was also studied. It was found that aging influenced the microstructure of the Ti6Al4V parts, including β, α, and α″ precipitation and fragmentation or globularization of elongated α grains. The aging process at 550 °C leads to an increase in tensile strength and a decrease in ductility.     

Recognition of the antigen-presenting molecule MR1 by a Vδ3+ γδ T cell receptor

Unlike conventional αβ T cells, γδ T cells typically recognize nonpeptide ligands independently of major histocompatibility complex (MHC) restriction. Accordingly, the γδ T cell receptor (TCR) can potentially recognize a wide array of ligands; however, few ligands have been described to date. While there is a growing appreciation of the molecular bases underpinning variable (V)δ1⁺ and Vδ2⁺ γδ TCR-mediated ligand recognition, the mode of Vδ3⁺ TCR ligand engagement is unknown. MHC class I–related protein, MR1, presents vitamin B metabolites to αβ T cells known as mucosal-associated invariant T cells, diverse MR1-restricted T cells, and a subset of human γδ T cells. Here, we identify Vδ1/2⁻ γδ T cells in the blood and duodenal biopsy specimens of children that showed metabolite-independent binding of MR1 tetramers. Characterization of one Vδ3Vγ8 TCR clone showed MR1 reactivity was independent of the presented antigen. Determination of two Vδ3Vγ8 TCR-MR1-antigen complex structures revealed a recognition mechanism by the Vδ3 TCR chain that mediated specific contacts to the side of the MR1 antigen-binding groove, representing a previously uncharacterized MR1 docking topology. The binding of the Vδ3⁺ TCR to MR1 did not involve contacts with the presented antigen, providing a basis for understanding its inherent MR1 autoreactivity. We provide molecular insight into antigen-independent recognition of MR1 by a Vδ3⁺ γδ TCR that strengthens an emerging paradigm of antibody-like ligand engagement by γδ TCRs.

Characterized by both innate and adaptive immune cell functions, γδ T cells are an unconventional T cell subset. While the functional role of γδ T cells is yet to be fully established, they can play a central role in antimicrobial immunity (1), antitumor immunity (2), tissue homeostasis, and mucosal immunity (3). Owing to a lack of clarity on activating ligands and phenotypic markers, γδ T cells are often delineated into subsets based on the expression of T cell receptor (TCR) variable (V) δ gene usage, grouped as Vδ2⁺ or Vδ2⁻.The most abundant peripheral blood γδ T cell subset is an innate-like Vδ2⁺subset that comprises ∼1 to 10% of circulating T cells (4). These cells generally express a Vγ9 chain with a focused repertoire in fetal peripheral blood (5) that diversifies through neonatal and adult life following microbial challenge (6, 7). Indeed, these Vγ9/Vδ2⁺ T cells play a central role in antimicrobial immune response to Mycobacterium tuberculosis (8) and Plasmodium falciparum (9). Vγ9/Vδ2⁺ T cells are reactive to prenyl pyrophosphates that include isopentenyl pyrophosphate and (E)-4-Hydroxy-3-methyl-but-2-enyl pyrophosphate (8) in a butyrophilin 3A1- and BTN2A1-dependent manner (10–13). Alongside the innate-like protection of Vγ9/Vδ2⁺ cells, a Vγ9⁻ population provides adaptive-like immunobiology with clonal expansions that exhibit effector function (14).The Vδ2⁻ population encompasses the remaining γδ T cells but most notably the Vδ1⁺ and Vδ3⁺ populations. Vδ1⁺ γδ T cells are an abundant neonatal lineage that persists as the predominating subset in adult peripheral tissue including the gut and skin (15–18). Vδ1⁺ γδ T cells display potent cytokine production and respond to virally infected and cancerous cells (19). Vδ1⁺ T cells were recently shown to compose a private repertoire that diversifies, from being unfocused to a selected clonal TCR pool upon antigen exposure (20–23). Here, the identification of both Vδ1⁺ T_naive and Vδ1⁺ T_effector subsets and the Vδ1⁺ T_naive to T_effector differentiation following in vivo infection point toward an adaptive phenotype (22).The role of Vδ3⁺ γδ T cells has remained unclear, with a poor understanding of their lineage and functional role. Early insights into Vδ3⁺ γδ T cell immunobiology found infiltration of Vδ3⁺ intraepithelial lymphocytes (IEL) within the gut mucosa of celiac patients (24). More recently it was shown that although Vδ3⁺ γδ T cells represent a prominent γδ T cell component of the gut epithelia and lamina propria in control donors, notwithstanding pediatric epithelium, the expanding population of T cells in celiac disease were Vδ1⁺ (25). Although Vδ3⁺ IELs compose a notable population of gut epithelia and lamina propria T cells (∼3 to 7%), they also formed a discrete population (∼0.2%) of CD4⁻CD8⁻ T cells in peripheral blood (26). These Vδ3⁺ DN γδ T cells are postulated to be innate-like due to the expression of NKG2D, CD56, and CD161 (26). When expanded in vitro, these cells degranulated and killed cells expressing CD1d and displayed a T helper (Th) 1, Th2, and Th17 response in addition to promoting dendritic cell maturation (26). Peripheral Vδ3⁺ γδ T cells frequencies are known to increase in systemic lupus erythematosus patients (27, 28), and upon cytomegalovirus (29) and HIV infection (30), although, our knowledge of their exact role and ligands they recognize remains incomplete.The governing paradigms of antigen reactivity, activation principles, and functional roles of γδ T cells remain unresolved. This is owing partly due to a lack of knowledge of bona fide γδ T cell ligands. Presently, Vδ1⁺ γδ T cells remain the best characterized subset with antigens including Major Histocompatibility Complex (MHC)-I (31), monomorphic MHC-I–like molecules such as CD1b (32), CD1c (33), CD1d (34), and MR1 (35), as well as more diverse antigens such as endothelial protein coupled receptor (EPCR) and phycoerythrin (PE) (36, 37). The molecular determinants of this reactivity were first established for Vδ1⁺ TCRs in complex with CD1d presenting sulfatide (38) and α-galactosylceramide (α-GalCer) (34), which showed an antigen-dependent central focus on the presented lipids and docked over the antigen-binding cleft.In humans, mucosal-associated invariant T (MAIT) cells are an abundant innate-like αβ T cell subset typically characterized by a restricted TCR repertoire (39–43) and reactivity to the monomorphic molecule MR1 presenting vitamin B precursors and drug-like molecules of bacterial origin (41, 44–46). Recently, populations of atypical MR1-restricted T cells have been identified in mice and humans that utilize a more diverse TCR repertoire for MR1-recognition (42, 47, 48). Furthermore, MR1-restricted γδ T cells were identified in blood and tissues including Vδ1⁺, Vδ3⁺, and Vδ5⁺ clones (35). As seen with TRAV 1-2⁻, unconventional MAITs cells the isolated γδ T cells exhibited MR1-autoreactivity with some capacity for antigen discrimination within the responding compartment (35, 48). Structural insight into one such MR1-reactive Vδ1⁺ γδ TCR showed a down-under TCR engagement of MR1 in a manner that is thought to represent a subpopulation of MR1-reactive Vδ1⁺ T cells (35). However, biochemical evidence suggested other MR1-reactive γδ T cell clones would likely employ further unusual docking topologies for MR1 recognition (35).Here, we expanded our understanding of a discrete population of human Vδ3⁺ γδ T cells that display reactivity to MR1. We provide a molecular basis for this Vδ3⁺ γδ T cell reactivity and reveal a side-on docking for MR1 that is distinct from the previously determined Vδ1⁺ γδ TCR-MR1-Ag complex. A Vδ3⁺ γδ TCR does not form contacts with the bound MR1 antigen, and we highlight the importance of non–germ-line Vδ3 residues in driving this MR1 restriction. Accordingly, we have provided key insights into the ability of human γδ TCRs to recognize MR1 in an antigen-independent manner by contrasting mechanisms.