Solid state NMR characterization of lithium conducting ceramics

⁷Li solid state NMR has been used to characterize lithium aluminium titanium phosphate and lithium lanthanum titanate ceramics. Both materials have high ionic mobilities at room temperature and this is reflected in their static ⁷Li powder patterns. In the case of the phosphate based ceramic, a narrow Lorentzian peak is observed above 300 K, which narrows further with increasing temperature. The accompanying quadrupolar structure, with C_Q (quadrupolar coupling constant) ~ 40 kHz, suggests that the lithium ions are hopping rapidly between equivalent, high electric field gradient sites. The ²⁷Al and ³¹P magic angle spinning (MAS) spectra reveal an asymmetric phosphorus peak and two distinct aluminium resonances. The room temperature powder pattern of Li_0.33La_0.57TiO₃ shows a dipolar broadened peak which narrows quite suddenly at 310 K revealing quadrupolar satellites with C_Q ~ 900 Hz. A second lithium site is also observed in this material, as indicated by a further, weaker quadrupolar structure (C_Q ~ 40 kHz).

Effect of relaxation on pressure sensitivity index in a Zr-based metallic glass

Shear-banding features of as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass were investigated through Rockwell indentation tests. Isothermal annealing of the as-cast samples was conducted at temperatures below its glass transition temperature, Tg. The exothermal enthalpy during continuous heating below Tg decreases with increasing annealing temperature, indicating the gradual reduction of free-volume upon annealing. The observation on the morphology of shear-banding pattern around the indents implies a reduced shear bands activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of Rockwell indent decrease from 88° for the as-cast sample to 79° for the sample annealed at 633 K for 1 h, indicating a pressure sensitive plasticity. By Mohr–Coulomb criterion, the pressure sensitive index can be obtained on the basis of the measured 2θ, which increases with increasing annealing temperature, indicating an increase of “atomistic friction” due to the reduction of the free volume upon annealing.

Indentation study on the pressure sensitivity of a ZR-based bulk metallic glass

Spherical indentation test was conducted on as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass, and the evolution of the morphology of the deformation zone of indents upon annealing was investigated. The DSC traces of the as-cast and annealed samples show that the enthalpy change at the glass transition, ΔH, decreases with the increasing of annealing temperature, indicating the reduction of the free volume upon annealing. The morphology of the indents implies a reduced shear band activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of spherical indent in the as-cast and the annealed samples were measured to be in the range of 88-79°, which decrease with the increasing of annealing temperature, indicating pressure sensitive plasticity in the as-cast and annealed samples. By Mohr–Coulomb criterion, the pressure sensitive index, α, can be obtained on the basis of the measured 2θ. The sensitivity index increases with increasing temperature, implying an increase of 'atomistic friction' due to the reduction of the free volume upon annealing.

Mg-based metallic glass / titanium interpenetrating phase composite with high mechanical performance

We report an Mg-based metallic glass/titanium interpenetrating phase composite in which constituent phases form a homogeneously interconnected network. The porous titanium constrains shear bands propagation thoroughly and promotes shear bands branching and intersection subsequently. The homogeneous phase distribution promotes regularly distributed local shear deformation and leads to a uniform deformation for the composites. Moreover, the interpenetrating phase structure introduces a mutual-reinforcement between metallic glass and titanium. Therefore, the composite exhibits excellent mechanical performance with compressive fracture strength of 1783 MPa and fracture strain of 31%.

Extrusion properties of a Zr-based bulk metallic glass

The extrusion behavior of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 metallic glasses in the supercooled liquid region was investigated. Good extrusion formability was observed under low strain rates at temperatures higher than 395 °C. The metallic glasses were fully extruded without crystallization and failure within the range of T=395–415 °C under strain rates from 5×10⁻³ s⁻¹ to 5×10⁻² s⁻¹, and the deformation behavior of the metallic glasses during the extrusion was found to be in a Newtonian viscous flow mode by a strain rate sensitivity of 1.0.

Compressive deformation and damage of Mg-based metallic glass interpenetrating phase composite containing 30-70 vol% titanium

Mg-based metallic glass interpenetrating phase composites (IPCs) containing 30-70 vol% titanium was fabricated in this study. The effects of reinforced phase volume fraction and interspace on the mechanical properties were investigated systematically. With increasing the volume fraction of titanium, the fracture strength and strain increased up to 1860 MPa and 44%, respectively. The results showed that the critical volume fraction (around 40%) of Ti metal should be required for significantly improving plasticity of IPC. Decreasing the interspace of the titanium phase could lead to enhancement of yield and fracture strength. The deformation behavior and strengthening mechanisms were discussed in detail.

Composition dependency of the glass forming ability (GFA) in Mg—Ni—Si system by mechanical alloying

The pure elemental powder mixtures with the compositions of Mg₆₅Ni_xSi₃₅−_x (x = 10, 20, 25, 33 at.%) were subject to high-energy ball mill, and the structures of the mixtures at different intervals of milling were characterised by X-ray diffraction (XRD). The compositional dependency of the glass forming ability (GFA) in Mg–Ni–Si system was evaluated based on the experimental results and the theoretical calculation. The compositional dependency of GFA in Mg–Ni–Si system can be understood well by comparing the enthalpies of the crystalline and amorphous phases based on the Miedema's theory for the formation enthalpy of alloys. Increasing the Ni/Mg ratio and/or decreasing Si content can improve the amorphous formability. The calculation results might be of great help in optimising the composition with high GFA in Mg–Ni–Si system.

Effect of structure relaxation on the plastic deformation behaviour in a Zr-based BMG under indenter

Vickers and nano indentations were performed on a structurally relaxed Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass (BMG), and the evolution of the shear bands in the relaxed BMG was investigated and compared to that in the as-cast alloy. Results indicate that the plastic deformation in the BMG with structure relaxation is accommodated by the semicircular (primary) and radial (secondary) as well as tertiary shear bands. Quantitatively, the shear band density in the relaxed alloy was much lower than that in the as-cast alloy. The annihilation of free volume caused by the annealing was responsible for the embrittlement of the sample with structure relaxation.

Plastic deformation in a partially crystallized Zr-based BMG under Vickers indenter

Vickers indentations were carried out on an anneal-introduced partially crystallized Zr₄₁Ti₁₄Cu_12.5 Ni₁₀Be_22.5 bulk metallic glass (BMG), and the evolution of the shear bands in this samplewas investigated and compared to the as-cast, aswell as the structurally relaxed counterparts. The results indicate that the plastic deformation in the partially crystallized BMG was accommodated by the semi-circular (primary) and radial (secondary) shear bands. A full crack or flake that was produced due to the spring back during the load removal was observed. The shear band density in the annealed alloy which was dispersed with crystalliteswas significantly lower than that of the as-cast alloy. The difference of the shear band features among the three kinds of alloy status, i.e., partially crystallized, structurally relaxed and as-cast alloys was discussed in terms of the free volume in the BMGs and the characteristics of nano-composites. It has been demonstrated that the plasticity for the three statuses of alloys queues in the descending order as the as-cast, annealed with partial crystallization, and annealed without crystallization.

The enhancement of lithium ion dissociation in polyelectrolyte gels on the addition of ceramic nano-fillers

Nano-particle oxide fillers including TiO₂, SiO₂ and Al₂O₃ have previously been shown to have a significant affect on the properties of both polymer and polymer gel electrolytes. In some cases, conductivity increases of one order of magnitude have been reported in crystalline PEO–base complexes. In this work, we report the effects of TiO₂ and SiO₂ on a poly(Li-AMPS)-based gel polyelectrolyte. Impedance spectroscopy and pfg-NMR spectroscopy indicates an increase in the number of available charge carriers with the addition of filler. An ideal amount of ceramic filler has been identified, with additional filler only saturating the system and reducing the conductivity below that of the pristine polyelectrolyte system. SEM micrographs suggest a model whereby the filler interacts readily with the sulfonate group; the surface area of the filler being an important factor.

Lithium ion mobility in poly(vinyl alcohol) based polymer electrolytes as determined by 7Li NMR spectroscopy

Solvent-free polymer electrolytes based on poly(vinyl alcohol) (PVA) and LiCF₃SO₃ have shown relatively high conductivities (10⁻⁸-10⁻⁴ S cm⁻¹), with Arrhenius temperature dependence below the differential scanning calorimeter (DSC) glass transition temperature (343 K). This behaviour is in stark contrast to traditional polymer electrolytes in which the conductivity reflects VTF behaviour. ⁷Li nuclear magnetic resonance (NMR) spectroscopy has been employed to develop a better understanding of the conduction mechanism. Variable temperature NMR has indicated that, unlike traditional polymer electrolytes where the linewidth reaches a rigid lattice limit near T_g, the lithium linewidths show an exponential decrease with increasing temperature between 260 and 360 K. The rigid lattice limit appears to be below 260 K. Consequently, the mechanism for ion conduction appears to be decoupled from the main segmental motions of the PVA. Possible mechanisms include ion hopping, proton conduction or ionic motion assisted by secondary polymer relaxations.