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In a lithium-ion battery, both electrodes are atomic frameworks that host mobile lithium ions. When the battery is being charged or discharged, lithium ions diffuse from one electrode to the other. Such an insertion reaction deforms the electrodes and may cause the electrodes to crack. This paper uses fracture mechanics to determine the critical conditions to avert insertion-induced cracking. The method is applied to cracks induced by the mismatch between phases in LiFePO4.
BaCo1/3Nb2/3O3 ceramics, with a high density and a similar, high degree of 1:2 B-site cation ordering, exhibit very different quality factors, Q. The ceramics exhibit p-type behavior with higher conductivity and lower Q for samples processed in O2 as compared with those processed in air. It is proposed that unavoidable Co loss during high-temperature ceramic processing leads to p-type doping that must be compensated by oxygen vacancies to impede hole formation. The composition exhibiting only intrinsic conduction and optimized Q is not achieved with processing in atmospheric oxygen due to filling of oxygen vacancies and hole formation during cooling.
The deformation behavior of amorphous selenium near its glass transition temperature (31 °C) has been investigated by uniaxial compression and nanoindentation creep tests. Cylindrical specimens compressed at high temperatures and low strain rates deform stably into barrel-like shapes, while tests at low temperatures and high strain rates lead to fragmentation. These results agree well with stress exponent and kinetic activation parameters extracted from nanoindentation creep tests using a similarity analysis. The dependence of the deformation modes on temperature and strain rate can be understood as a consequence of material instability and strain localization in rate-dependent solids.
Application of high intensity electric pulse (HIEP) to a severely deformed eutectoid microstructure in high carbon steel wire has resulted in spheroidized microstructure. The observed spheroidization on electropulsing is compared with that reported for isothermal/thermo-mechanical annealing of the pearlite structure. The faster kinetics observed in this study has been rationalized in terms of accelerated kinetics induced by HIEP.
Applying the glass fluxing method, a peritectic Fe–Ni alloy with a composition of Fe–4.35 at.% Ni was undercooled. It was found that when the initial melt undercooling (ΔT) is smaller than 130 K, the overall thickness of the peritectic phase formed in peritectic reaction (PR) and peritectic transformation (PT) decreases as ΔT increases. The nonequilibrium effects of the primary solidification on PR and PT in the undercooled peritectic Fe–Ni alloys were illuminated. With increasing ΔT, since the driving forces for PR and PT change slightly, the decrease of the overall thickness of the peritectic phase formed in PR and PT can be mainly ascribed to the reduced transformation time for PT.
To investigate the effects of substituting Ag and Sb for Pb on the thermoelectric properties of PbTe, the electronic structures of PbTe and AgPb18SbTe20 were calculated by using the linearized augmented plane wave based on the density-functional theory of the first principles. By comparing the differences in the band structure, the partial density of states (PDOS), the scanning transmission microscope, and the electron density difference for PbTe and AgPb18SbTe20, we explained the reason from the aspect of electronic structures why the thermoelectric properties of AgPb18SbTe20 could be improved significantly. Our results suggest that the excellent thermoelectric properties of AgPb18SbTe20 should be attributed in part to the narrowing of its band gap, band structure anisotropy, the much extrema and large DOS near Fermi energy, as well as the large effective mass of electrons. Moreover, the complex bonding behaviors for which the strong bonds and the weak bonds are coexisted, and the electrovalence and covalence of Pb–Te bond are mixed should also play an important role in the enhancement of the thermoelectric properties of the AgPb18SbTe20.
The AlGaN-based ultraviolet (UV) light-emitting diode (LED) structures with AlN as buffer were grown on sapphire substrate by metalorganic vapor-phase epitaxy (MOVPE). A series of cathodoluminescence (CL) spectra were measured from the cross section of the UV-LED structure using point-by-point sampling to investigate the origins of the broad parasitic emissions between 300 and 400 nm, and they were found to come from the n-type AlGaN and AlN layers rather than p-type AlGaN. The parasitic emissions were effectively suppressed by adding an n-type AlN as the hole-blocking layer. Electroluminescence (EL) and atomic force microscopy (AFM) measurements have revealed that the interface abruptness and crystalline quality of the UV-LED structure are essential for the achievement of the EL emissions from the multiple quantum wells (MQWs).
Thornlike Tb-doped SiC (SiC:Tb) nanostructures were synthesized through a carbothermal reduction of electrospun Tb-doped SiO2 nanofibers (SiO2:Tb). The synthesized SiC nanostructures annealed at a high temperature of 1300 °C displayed a unique morphology and a high crystalline quality with the β-SiC phase. Strong green-light emissions were detected from the SiC:Tb samples. Photoluminescence excitation results show that, besides a small amount of energy coming from the SiC cores (464 nm), most of the energy needed for the excitation of Tb3+ ions comes from the light absorption of the SiO2–Tb surface layers (295 nm) and near-interface regions in the samples (388 nm). Transmission electron microscopy, energy dispersive spectrometry, and Raman analyses suggested that the formations of Tb clusters and SiO2 surface layers are very important to the enhancement of the luminescence behaviors of Tb3+ ions. Finally, we have constructed an excitation model and further proposed an energy transfer mechanism for these thornlike SiC:Tb nanostructures.
A late porogen removal scheme was used to make low-k materials (k = 2.72 to 2.02) using methylsilsesquioxane (MSQ) and a high-temperature porogen, poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), to circumvent the reliability issues related to as-deposited porous dielectric. Based on the nanoindentation and Fourier transform infrared spectroscopy (FTIR) analysis, the moduli of the hybrid films were found to be higher than their porous forms, and even better than the dense MSQ film, for porogen loading below a critical level (˜69.5 vol%). This could be attributed to their enhanced degree of cross-linking in MSQ as evidenced by the network/cage structural ratios. Besides, high-temperature porogen plays different roles during the cross-linking of MSQ depending on its loadings. In this study, with immediate loading at 16.7 vol%, PS-b-P4VP can serve as plasticizer to enhance the degree of cross-linking, but at a large loading >16.7 vol%, it becomes a steric hindrance reducing the degree of cross-linking.
Holmium-doped BaTiO3 with composition Ba0.97Ho0.03TiO3 was prepared by sol-gel combustion method. A molar ratio of citrate/nitrate (CA/NO3− = 1.3) was used to prepare nanopowders of (Ba,Ho)TiO3. The structure and microstructure of (Ba,Ho)TiO3 powders and ceramics were investigated. The ceramics exhibit a dielectric constant of about 4400 and dielectric loss (tan δ = 0.267) at 10 Hz, and at the Curie temperature (Tc = 132 °C). The remanent polarization and the coercive field of Ba0.97Ho0.03TiO3 ceramics, at 1 kHz, were Pr = 6 μC/cm2 and EC = 0.75 kV/cm. The dielectric and ferroelectric behavior of the holmium-doped BaTiO3 is influenced by the amphoteric character of Ho3+ ions.
BaTiO3 thin films were prepared on metallic foil substrates using chemical solution deposition. The impact of A to B site cation ratios on the phase assemblage and microstructural and dielectric properties was investigated by characterizing a sample set that includes stoichiometric BaTiO3 and 1, 2, 3, 4, and 5 mol% excess BaO. Each composition was subjected to a high-temperature anneal step with maximum dwell temperatures of 1000, 1100, and 1200 °C for 20 h. Excess barium concentrations greater than 3% lead to dramatic grain growth and average grain sizes exceeding 1 μm. Despite the large deviations from stoichiometry and the 20 h dwell time at temperature, x-ray diffraction, and high-resolution electron microscopy analysis were unable to detect secondary phases until films with 5% excess barium were annealed to 1200 °C. Thin films with 3% excess barium were prepared on copper substrates and annealed at 1060 °C, the practical limit for copper. This combination of BaO excess and annealing temperature produced an average lateral grain size of 0.8 μm and a room-temperature permittivity of 4000. This is in comparison to a permittivity of 1800 for stoichiometric material prepared using identical conditions. This work suggests metastable solubility of BaO in BaTiO3 that leads to enhanced grain growth and large permittivity values. This technique provides a new solid-state means of achieving grain growth in low thermal budget systems.
Heteroepitaxial ZnxMg1−xO thin films were grown on lattice-matched MgO (100) substrates using radiofrequency plasma-assisted molecular-beam epitaxy. High-quality epilayers with zinc concentrations ranging from x = 0 (MgO) to x = 0.65 were grown and characterized optically, structurally, and electrically. The ZnxMg1−xO films were found to maintain the rocksalt cubic (B1) crystal structure for concentrations z < 0.65, with a linear dependence of lattice constant on Zn concentration. X-ray diffraction (XRD) also revealed the emergence of phase segregation into wurtzite (B4) phase for the highest concentration film. The band gap energy of the films was successfully varied from 4.9 to 6.2 eV (253–200 nm), showing a linear relationship with Zn concentration. The strictly cubic films exhibit roughness on the order of 10 Å and resistivities of approximately 106 Ω·cm.
Oxidation-induced stress evolutions in Ta thin films were investigated using ex situ microstructure analyses and in situ wafer curvature measurements. It was revealed that Ta thin films are oxidized to a crystalline TaO2 layer, which is subsequently oxidized to an amorphous tantalum pentoxide (a-Ta2O5) layer. Initial layered oxidation from Ta to TaO2 phases abruptly induces high compressive stress up to about 3.5 GPa with fast diffusion of oxygen through the Ta layer. Subsequently, it is followed by stress relaxation with the oxidation time, which is related to the slow oxidation from TaO2 to Ta2O5 phases. The initial compressive stress originates from the molar volume expansion during the layered formation of TaO2 from the Ta layer, while the relaxation of the compressive stresses is ascribed to the amorphous character of the a-Ta2O5 layer. According to Kissinger's analysis of the stress evolution during an isochronic heating process, the oxygen diffusion process through the a-Ta2O5 layer is the rate-controlling stage in the layered oxidation process of forming a a-Ta2O5/TaO2/Ta multilayer and has an activation energy of about 190.8 kJ/mol.
Blister features produced by laser-induced delamination of silicon dioxide from silicon substrates were analyzed with thin-film buckling mechanics. These analyses revealed the role of the interaction between the material and the femtosecond (fs)-pulsed laser on blister formation. In particular, it was deduced that the magnitude of the compressive residual film stress within the irradiated region appeared to exceed the intrinsic residual stress obtained from wafer curvature techniques. This apparent increase in the compressive stress after fs-pulsed laser irradiation may be caused by a modification of the oxide, which resulted in a local rarefaction of the film. The results demonstrated important features of the interaction between materials and fs-pulsed laser, including the presence of subtle modification thresholds and the limited role of thermal effects.
Nitrogen-doped titania with a unique two-level hierarchical structure and visible light photocatalytic activity is reported. Thus, nitrogen-doped titanium oxide microrods decorated with N-doped titanium oxide nanosheets were synthesized by a hydrothermal reaction in NH4OH and postcalcination. During the calcination, the in situ incorporation of nitrogen atoms of ammonium ion into titania lattice was accompanied by the structural evolution from titanate to anatase titania. The morphological and structural evolution was monitored by scanning electron microscopy (SEM), x-ray diffraction (XRD), thermogravimetric analysis/differential thermal analysis (TGA/DTA), Raman, Fourier transform infrared (FTIR), x-ray absorption near edge structure (XANES), x-ray photoelectron spectroscopy (XPS), and adsorption isotherms. The N-doping brought visible light absorption, and the material exhibited high photocatalytic activity in the decomposition of Orange II under visible light irradiation (λ ≥ 400 nm), especially when it was loaded with 1 wt% Pt as a cocatalyst.
Polymer gels have potential use for a wide variety of applications, primarily due to the ability to tailor the gel properties by varying several material parameters. While substantial attention has focused on water-based hydrogels, the use of these materials is limited due to a narrow operational temperature range. This report describes a nonaqueous polymer gel, composed of a cross-linked polybutadiene network swollen with low volatility polymer plasticizers. Thermal, mechanical, and adhesive characterization illustrated that the gels exhibit performance over an extremely broad temperature range (−60–70 °C). Solvent quality and loading played a critical role in the operational temperature window with small solvent solubility parameter deviations dramatically reducing the operational temperature range. In addition, the processing conditions had a large impact on the gel mechanical properties. As a result, it is important to consider the influence of processing conditions and solvent quality when tailoring polymer gels for practical applications.
We report the quasistatic tensile and impact penetration properties (falling dart test) of injection-molded polycarbonate samples, as a function of multiwall carbon nanotube (MWNT) concentration (0.0–2.5%). The MWNT were incorporated by dilution of a commercial MWNT/polycarbonate masterbatch. The stiffness and quasistatic yield strength of the composites increased approximately linearly with MWNT concentration in all measurements. The energy absorbed in fracture was, however, a negative function of the MWNT concentration, and exhibited different dependencies in quasistatic and impact tests. Small-angle x-ray scattering (SAXS) showed that the dispersion of the MWNT was similar at all concentrations. The negative effects on energy absorption are attributed to agglomerates remaining in the samples, which were observed in optical microscopy and SAXS. Overall, there was a good correspondence between static and dynamic energy absorption.
In our previous study, we modeled the indentation performed on an elastic–plastic solid with a rigid conical indenter by using finite element analysis, and established a relationship between a nominal hardness/reduced Young’s modulus (Hn/Er) and unloading work/total indentation work (We/Wt). The elasticity of the indenter was absorbed in Er ≡ 1/[(1 − ν2)/E + (1 − νi2)/Ei], where Ei and νi are the Young’s modulus and Poisson’s ratio of the indenter, and E and ν are those of the indented material. However, recalculation by directly introducing the elasticity of the indenter show that the use of Er alone cannot accurately reflect the combined elastic effect of the indenter and indented material, but the ratio η = [E/(1 − ν2)]/[Ei/(1 − νi2)] would influence the Hn/Er–We/Wt relationship. Thereby, we replaced Er with a combined Young’s modulus Ec ≡ 1/[(1 − ν2)/E + 1.32(1 − νi2)/Ei] = Er/[1 + 0.32η/(1 + η)], and found that the approximate Hn/Ec–We/Wt relationship is almost independent of selected η values over 0–0.3834, which can be used to give good estimates of E as verified by experimental results.
The purpose of this study is to experimentally investigate the interaction of inelastic deformation and microstructural changes of two Zr-based bulk metallic glasses (BMGs): Zr41.25Ti13.75Cu12.5Ni10Be22.5 (commercially designated as Vitreloy 1 or Vit1) and Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy 4, Vit4). High-temperature uniaxial compression tests were performed on the two Zr alloys at various strain rates, followed by structural characterization using differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Two distinct modes of mechanically induced atomic disordering in the two alloys were observed, with Vit1 featuring clear phase separation and crystallization after deformation as observed with TEM, while Vit4 showing only structural relaxation with no crystallization. The influence of the structural changes on the mechanical behaviors of the two materials was further investigated by jump-in-strain-rate tests, and flow softening was observed in Vit4. A free volume theory was applied to explain the deformation behaviors, and the activation volumes were calculated for both alloys.
Zr65Al7.5Ni10Cu12.5Nb5 glass was found to exhibit a large plastic compressive strain of over 10% and the property was suggested to be due to deformation-induced nanocrystallization. A transmission electron microscopic observation, however, only revealed obscure ordered clusters with a size of ˜2 nm in the fracture surface of a deformed sample, instead of well-identified crystals as previously reported for the Zr–Al–Ni–Cu–Pd system. This phenomenon is suggested to correlate with the higher viscosity of supercooled liquid and the slower grain growth of icosahedral phase during primary crystallization in the Zr65Al7.5Ni10Cu12.5Nb5 compared to those in the Zr65Al7.5Ni10Cu12.5Pd5 alloy. The role of the deformation-induced nanoclusters on the enhanced compressive plasticity was discussed.