Sintering and annealing effects on ZnO microstructure and thermoelectric properties

The influence of different thermal treatments on zinc oxide has been investigated regarding the thermal diffusivity and structural properties of doped and undoped samples. ZnO powders having various grain sizes and morphologies, with or without aluminum doping, have been prepared under different temperatures by spark plasma sintering (SPS). The microstructural properties and thermal diffusivities of the prepared samples have been measured before and after annealing treatments in air at 800 °C. In undoped samples, the crystallite sizes increased after the annealing treatments, while it was retained in the Al-doped samples. The thermal diffusivities, microstrain and degree of preferred orientation were affected by the SPS temperature and the annealing; however, the general trends were retained after the annealing treatments. Lower maximum temperature yielded a lower degree of preferred orientation, less microstrain, higher density of grain boundaries, lower thermal diffusivities and, for Al-doped samples, lower electrical conductivity and a difference in zT-values from 0.2 to 0.3 at 800 °C. Calculations of the wavelengths and mean free paths of the phonons that contribute to the main part of the thermal conductivity have been conducted and reveal that nanostructures <12 nm are required to lower the thermal conductivity by quantum confinement.     

Experimental investigation and modeling of the influence of microstructure on the resistive conductivity of a Cu–Ag–Nb in situ composite

A Cu–8.2 wt% Ag–4 wt% Nb in situ metal matrix composite was manufactured by inductive melting, casting, swaging, and wire drawing. The final wire (η=ln(A₀/A)=10.5, A: wire cross section) had a strength of 1840 MPa and 46% of the conductivity of pure Cu. The electrical resistivity of the composite wires was experimentally investigated as a function of wire strain and temperature. The microstructure was examined by means of optical and electron microscopy. The observed decrease in conductivity with increasing wire strain is interpreted in terms of inelastic electron scattering at internal phase boundaries. The experimental data are in very good accord with the predictions of an analytical size-effect model which takes into account the development of the filament spacing as a function of wire strain and the mean free path of the conduction electrons as a function of temperature. The experimentally obtained and calculated resistivity data are compared to those of the pure constituents.     

Microstructure and mechanical properties of ultrafine-grained fcc/hcp cobalt processed by a bottom-up approach

Bulk Co samples having a mean grain size of ～300 nm were processed by hot isostatic pressing of a high purity Co nanopowder synthesized by chimie douce. The grain interior exhibited a highly faulted nanoscale lamellar microstructure comprising an intricate mixture of face-centered cubic, hexagonal close-packed phases and nanotwins. Room temperature compression tests carried out at a strain rate of ～2 × 10^?4 s^?1 revealed a yield stress of ～1 GPa, a strain to rupture of ～5%. During straining it was found that the hexagonal close-packed phase content increased from 55% to 65% suggesting a deformation mechanism based on stress-assisted face-centered cubic to hexagonal close-packed phase transformation. In addition, an apparent activation volume of ～3b³ was computed which indicates that the deformation mechanism was controlled by dislocation nucleation from the numerous boundaries. Nonetheless, in such an intricate microstructure, the overall mechanical properties are discussed in term of a complex interplay between lattice dislocation plasticity, transformation-induced plasticity and possibly twin-induced plasticity.     

Study of LiMgVO4 electrical conductivity mechanism

This paper deals with impedance spectroscopy on single-phase polycrystalline LiMgVO₄ in the temperature range of 25–500 °C. Thermogravimetric measurements show a weight loss of 2.7% in the temperature range between 25 °C and 175 °C due to humidity desorption. A conductivity mechanism along the grain boundaries (agb) is identified in the specific temperature range and is attributed to a reversible humidity absorption–desorption mechanism. Equivalent circuits are drawn using the results of the impedance measurements at each temperature. A unique conduction process within the material is assigned to each element of the equivalent circuit and Arrhenius plots are plotted. The calculation of activation energy of each conduction mechanism is based on the Arrhenius plots. The activation energy E_b of the bulk conductivity mechanism was found to be 0.62 eV. The activation energy E_gb of the grain boundaries conductivity mechanism was found to be 1.03 eV up to 275 °C and 0.50 eV in the temperature range of 300–500 °C. The absence of the conductivity mechanism along the grain boundaries above 175 °C can only be due to the complete removal of water from the material's grains.     

Simultaneously optimizing the independent thermoelectric properties in (Ti,Zr,Hf)(Co,Ni)Sb alloy by in situ forming InSb nanoinclusions

We report an induction-melting spark-plasma-sintering synthesis process of the nanocomposite material composed of (TiZrHf)(CoNi)Sb coarse grains and in situ formed InSb nanoinclusions that occur primarily on the grain boundaries. We were able to qualitatively control the amount of InSb nanoinclusions by varying the In and Sb contents in the starting materials. The effects of the nanoinclusion formation and the matrix–nanoinclusion boundaries on the thermoelectric properties have been studied and correlated. In particular, the nanoinclusion-induced electron injection and electron filtering mechanisms helped to simultaneously decrease the resistivity, enhance the Seebeck coefficient and reduce the thermal conductivity of the nanocomposite. A figure of merit of ZT ～ 0.5 was attained at 820 K for the sample containing 1 at.% InSb nanoinclusions, which is a 160% improvement over the sample containing no nanoinclusions. The experimental results are discussed in the context of the effective medium model formerly proposed by Bergman and Fel.     

Peculiar size effect in nanocrystalline BaTiO3

Dense BaTiO₃ ceramics with grain sizes of 35 nm to 5.6 μm were prepared, and the electrical properties investigated in the temperature range 500–700 °C by means of impedance spectroscopy. Charge carriers (oxygen vacancies and holes) are depleted in the space charge regions at the BaTiO₃ grain boundaries. When the grain size is ?250 nm, the width of the space charge region was determined to be ～40 nm. Therefore, the depletion regions were expected to overlap when the grain size decreases to 35 nm; in such a situation, charge carriers would be depleted over the entire grain, resulting in depressed conductivity. However, the conductivity of the 35 nm grain size sample was measured to be one to two orders of magnitude higher than those of the microcrystalline samples, and the activation energy markedly lower. Moreover, we determined a width of ～7 nm for the space charge regions in the 35 nm grain size sample; therefore, the space charge regions do not overlap. The enhanced conductivity is ascribed to a reduced oxidation enthalpy in nanocrystalline BaTiO₃, and the distorted grain boundaries in nanocrystalline BaTiO₃ are believed to be the atomic level origin of the reduced oxidation enthalpy.     

Microstructural characteristics of tungsten-base nanocomposites produced from micropowders by high-pressure torsion

Micropowder mixtures of W–50% Al, W–50% Ti and W–50% Ni were subjected to severe plastic deformation at 573 K using high-pressure torsion (HPT). The powder mixtures were consolidated and nanocomposites of W/Ti, W/Ti and W/Ni, with average grain sizes as small as ～9, ～15 and ～12 nm, respectively, were formed by imposing large shear strains. The nanocomposites exhibited Vickers microhardness as high as ～900 Hv, a level that has rarely been reported for metal–matrix composites. X-ray diffraction analyses together with high-resolution transmission electron microscopy showed that in addition to grain refinement, an increase in the fraction of grain boundaries up to 20%, the dissolution of elements in each other up to ～15 mol.%, an increase in the lattice strain up to 0.6%, and an increase in density of edge dislocations up to 10¹⁶ m^?2 occurred by HPT. The current study introduces the HPT process as an effective route for the production of ultrahigh-strength W-base nanocomposites, fabrication of which is not generally easy when processing at high temperatures because of interfacial reaction and formation of brittle intermetallics.     

In situ TEM study of microplasticity and Bauschinger effect in nanocrystalline metals

In situ transmission electron microscopy straining experiments with concurrent macroscopic stress–strain measurements were performed to study the effect of microstructural heterogeneity on the deformation behavior of nanocrystalline metal films. In microstructurally heterogeneous gold films (mean grain size d_m = 70 nm) comprising randomly oriented grains, dislocation activity is confined to relatively larger grains, with smaller grains deforming elastically, even at applied strains approaching 1.2%. This extended microplasticity leads to build-up of internal stresses, inducing a large Bauschinger effect during unloading. Microstructurally heterogeneous aluminum films (d_m = 140 nm) also show similar behavior. In contrast, microstructurally homogeneous aluminum films comprising mainly two grain families, both favorably oriented for dislocation glide, show limited microplastic deformation and minimal Bauschinger effect despite having a comparable mean grain size (d_m = 120 nm). A simple model is proposed to describe these observations. Overall, our results emphasize the need to consider both microstructural size and heterogeneity in modeling the mechanical behavior of nanocrystalline metals.     

Microstructural evolution and grain boundary sliding in a superplastic magnesium AZ31 alloy

Tensile experiments on a fine-grained single-phase Mg–Zn–Al alloy (AZ31) at 673 K revealed superplastic behavior with an elongation to failure of 475% at 1 × 10^?4 s^?1 and non-superplastic behavior with an elongation to failure of 160% at 1 × 10^?2 s^?1; the corresponding strain rate sensitivities under these conditions were ～0.5 and ～0.2, respectively. Measurements indicated that the grain boundary sliding (GBS) contribution to strain ξ was ～30% under non-superplastic conditions; there was also a significant sharpening in texture during such deformation. Under superplastic conditions, ξ was ～50% at both low and high elongations of ～20% and 120%; the initial texture became more random under such conditions. In non-superplastic conditions, deformation occurred under steady-state conditions without grain growth before significant flow localization whereas, under superplastic conditions, there was grain growth during the early stages of deformation, leading to strain hardening. The grains retained equiaxed shapes under all experimental conditions. Superplastic deformation is attributed to GBS, while non-superplastic deformation is attributed to intragranular dislocation creep with some contribution from GBS. The retention of equiaxed grain shapes during dislocation creep is consistent with a model based on local recovery related to the disturbance of triple junctions.     

Interfacial diffusion in Cu with a gradient nanostructured surface layer

A graded microstructure was produced in the surface layer of a pure Cu sample by means of surface mechanical attrition treatment (SMAT) [Wang K, Tao NR, Liu G, Lu J, Lu K. Acta Mater 2006;54:5281.]. The diffusion behavior of ⁶³Ni in such a surface layer was investigated by the radiotracer technique at temperatures <438 K. It is shown that the effective diffusivity in the top 10 μm surface layer is more than 2 orders of magnitude higher than that along conventional high-angle grain boundaries (HAGB) in Cu of similar purity. The diffusion rate increases gradually with increasing depth up to 30–50 μm, and then decreases with further increasing depth. The enhanced diffusivities reveal higher-energy states of various interfaces in the SMAT surface layer. The excess free energy of HAGB in this layer is estimated to be ～30% higher than that of conventional grain boundaries. An apparent retardation of the effective diffusion rate in the top 25 μm surface layer is induced by tracer leakage into numerous twin-boundary-like interfaces, while the gradual decrease in interface excess free energy correlates with the observed decrease in diffusivity in the subsurface layer at depths exceeding 50 μm.     

The formation of nanograin structures and accelerated room-temperature theta precipitation in a severely deformed Al–4 wt.% Cu alloy

The grain size achievable and long-term stability of a severely deformed aluminium copper alloy have been investigated when copper is used in solution to inhibit recovery. It is shown that copper is more effective than magnesium in inhibiting dynamic recovery. A grain width of only ～70 nm was obtained in an Al–4 wt.% Cu alloy, after processing by equal-channel angular extrusion to a strain of ε_eff = 10, resulting in a lamellar nanograin structure. However, post-processing, the severely deformed solid solution was found to be unstable at room temperature and copious precipitation of θ occurred at grain boundaries within the deformed state, leading to recovery of the deformation structure and a loss of strength. The solute level fell to equilibrium within ～9 months. The precipitation kinetics were shown to occur at many orders of magnitude higher than can be predicted by classical nucleation and growth theory. The reasons for this discrepancy are discussed.     

Structure and free volume of 〈1 1 0〉 symmetric tilt grain boundaries with the E structural unit

Atomistic simulations are used to investigate the structure and interfacial free volume of 〈1 1 0〉 symmetric tilt grain boundaries in copper containing the E structural unit from the Σ9(2 2 1)θ = 141.1° grain boundary. In this work, a stereologically-based methodology is used to calculate the grain boundary free volume along with the spacing and connectivity of free volume. After generating the minimum energy equilibrium grain boundary, we examine (i) the grain boundary structure, (ii) a measure of free volume associated with the grain boundary, (iii) spatial correlation functions of the distribution of free volume, and (iv) images of grain boundary free volume distribution. Using the results from these calculations, the influence of free volume spatial distribution and grain boundary structure on dislocation dissociation and nucleation is briefly discussed for boundaries with the E structural unit subjected to tensile loading normal to the interface along with the potential implications of free volume connectivity.     

Nanoquasicrystalline Al–Fe–Cr-based alloys. Part II. Mechanical properties

Nanoquasicrystalline Al-based alloys show considerable promise for elevated temperature applications compared with commercial Al-based alloys. In particular, a group of Al–Fe–Cr-based alloys-containing Ti, V, Nb or Ta have outstanding thermal stability. In the present work, the elevated temperature mechanical properties of these nanoquasicrystalline alloys were studied by tensile tests at a constant strain rate. Tests were designed in order to compare the mechanical behaviour at different test temperatures. Fractographic analysis was also carried out. The apparent activation energy for plastic deformation was found to be close to that for lattice self-diffusion for pure Al in the Al–Fe–Cr ternary alloy and in the Ti-containing alloy, and for grain boundaries diffusion for pure Al in the V-containing alloy, whereas the activation energy of the alloy with Ta additions was three times higher. All of the alloys showed similar sensitivity of plastic deformation to the strain rate in the range of 10^?3–5 × 10^?6 s^?1 at 350 °C. The apparent true stress exponent was n_app ～ 7, which can be associated with a deformation process controlled by dislocation mechanisms.     

Reduced thermal conductivity in Pb-alloyed AgSbTe2 thermoelectric materials

Pb-alloyed AgSbTe₂ (Pb_xAg₂₀Sb_30?xTe₅₀ (x = 3, 4, 5 and 6)) composites were synthesized using a modified Bridgman method with a graphite mold to form plate-like samples. The Bridgman-grown specimens were dense, with few solidification cavities, and were sufficiently mechanically robust for a variety of electronic/thermal transport measurements. Inhomogeneity was found on the grain boundary, and was embedded with the nanoprecipitates of δ-Sb₂Te with a feature size of 100 nm of the 5 at.% Pb and 6 at.% Pb specimens. A combined effect of alloying, inhomogeneity and nanoprecipitates leads to a low thermal conductivity of 0.3–0.4 W m^?1 K^?1, which approaches the theoretical minimum thermal conductivity of the amorphous material (κ_min ～ 0.36 W m^?1 K^?1). A peak of the zT value, ranging from 0.7 to 0.8, is achieved at 425 K. Further annealing at 673 K increases the grain size and causes a reduction in the value of the zT peak to 0.4.     

Generalized type III internal stress from interfaces,triple junctions and other microstructural components in nanocrystalline materials

The microstructure in polycrystalline materials consists of four types of geometric objects: grain cells, grain boundaries, triple junctions and vertex points. Each of them contributes to internal stress differently. Due to experimental limitations, the internal stresses associated with the microstructural components are difficult to acquire directly, particularly for polycrystalline materials with nanometer-scale grain sizes. Using newly developed computational methods, we obtained the type III internal stress associated with each of these microstructural objects in a stress-free nanocrystalline Cu. We found significant variation of the internal stresses from grain to grain, and their magnitudes descended in the order of vertex point, triple junction, grain boundary and grain cell. We also examined the effect of grain size and temperature. The change in the internal stresses inside the grains is found to follow a scaling relation of Ad^?x, using the mean grain diameter d from our results. For pressure, we found x = 1 and the effective interface stress A ～ 1 N m^?1, and for shear stress x = 0.75 and A ～ 14.12 N m^?1. On the other hand, the directly calculated interface stress is about 0.32–0.35 GPa for hydrostatic pressure and 12.45–12.60 GPa for von Mises shear stress. We discuss issues in treating the two-dimensional interface stress and one-dimensional triple junction line tension in nanocrystalline materials, as well as the potential impact of the type III internal stress on mechanical behavior of poly- and nano-crytalline materials.     

Void initiation in fcc metals: Effect of loading orientation and nanocrystalline effects

It is shown, through molecular dynamics simulations, that the emission and outward expansion of special dislocation loops, nucleated at the surface of nanosized voids, are responsible for the outward flux of matter, promoting their growth. Calculations performed for different orientations of the tensile axis, [0 0 1], [1 1 0] and [1 1 1], reveal new features of these loops for a face-centered cubic metal, copper, and show that their extremities remain attached to the surface of voids. There is a significant effect of the loading orientation on the sequence in which the loops form and interact. As a consequence, the initially spherical voids develop facets. Calculations reveal that loop emission occurs for voids with radii as low as 0.15 nm, containing two vacancies. This occurs at a von Mises stress approximately equal to 0.12G (where G is the shear modulus of the material), and is close to the stress at which dislocation loops nucleate homogeneously. The velocities of the leading partial dislocations are measured and found to be subsonic (～1000 m s^?1). It is shown, for nanocrystalline metals that void initiation takes place at grain boundaries and that their growth proceeds by grain boundary debonding and partial dislocation emission into the grains. The principal difference with monocrystals is that the voids do not become spherical and that their growth proceeds along the boundaries. Differences in stress states (hydrostatic and uniaxial strain) are discussed. The critical stress for void nucleation and growth in the nanocrystalline metal is considerably lower than in the monocrystalline case by virtue of the availability of nucleation sites at grain boundaries (von Mises stress ～0.05G). This suggests a hierarchy of nucleation sites in materials, starting with dispersed phases, triple points and grain boundaries, and proceeding with vacancy complexes up to divacancies.     

Crystal structure,morphology and physical properties of LaCo1−xTixO3±δ perovskites prepared by a citric acid assisted soft chemistry synthesis

The influence of the partial substitution of Co by Ti in the LaCoO₃ perovskite system is studied by evaluating the electrical conductivity, the Seebeck coefficient and the thermal conductivity of the compounds up to T = 1273 K. The X-ray diffraction patterns of the LaCo_1?xTi_xO_3±δ (0.01 ? x ? 0.5) phases show two structural modifications depending on the Ti content. Compounds with x < 0.3 crystallize in the rhombohedrally distorted perovskite structure while samples with x ? 0.3 possess an orthorhombic unit cell. The oxidation state of the Co ions is studied by X-ray absorption near edge structure (XANES) spectroscopy. A negative thermoelectric power is found in the LaCoO₃ system for low level Ti substitution (x = 0.01). In contrast, samples with higher Ti content show a large positive Seebeck coefficient, indicating positive majority charge carriers in the system. The electrical resistivity of the studied materials reveals a semiconducting-like behaviour. The lattice thermal conductivity was found to be low and nearly temperature-independent. The samples exhibit very small crystallite sizes in the range of few nanometres. Therefore, the low thermal conductivity can be assigned to an enhanced phonon scattering on grain boundaries.     

Superplasticity in electrodeposited nanocrystalline nickel

Electrodeposited nanocrystalline Ni films were processed with different levels of S, to evaluate the role of S on superplasticity. All the materials exhibited high strain rate superplasticity at a relatively low temperature of 777 K. Microstructural characterization revealed that the S was converted to a Ni₃S₂ phase which melts at 908 K; no S could be detected at grain boundaries. There was no consistent variation in ductility with S content. Superplasticity was associated with a strain rate sensitivity of ～0.8 and an inverse grain size exponent of ～1, both of which are unusual observations in superplastic flow of metals. Based on the detailed experiments and analysis, it is concluded that superplasticity in nano-Ni is related to an interface controlled diffusion creep process, and it is not related to the presence of S at grain boundaries or a liquid phase at grain boundaries.     

Attenuation of ultrasound in severely plastically deformed nickel

Ultrasound attenuation was measured in nickel specimens of about 30 mm diameter prepared using the high pressure torsion technique. The cold working process produced an equivalent shear strain increasing from zero at the center up to 1000% at the edge of the specimen. The fragmentation of the grains due to multiple dislocations led to an ultrafine microstructure with large angle grain boundaries. The mean value of the grain size distribution gradually decreased from ～50 μm at the center to 0.2 μm at the edge. Laser pulses of 5 ns were employed for the excitation of broadband ultrasound pulses covering the spectral range of 0.1–150 MHz. The ultrasound pulses were measured from the opposite side of the specimen by means of an optical interferometer and a piezoelectric foil transducer in two experimental setups. The features of the detected signal forms are discussed. The absolute value of the attenuation decreases from the center to the edge of the specimen showing nearly linear frequency dependence. The variation of the phase velocity was measured in a 6 mm-thick high pressure torsion nickel sample, revealing a velocity increase from the center to the edge.     

Texture,microstructure and mechanical properties of equiaxed ultrafine-grained Zr fabricated by accumulative roll bonding

The texture, microstructure and mechanical behavior of bulk ultrafine-grained (ufg) Zr fabricated by accumulative roll bonding (ARB) is investigated by electron backscatter diffraction, transmission electron microscopy and mechanical testing. A reasonably homogeneous and equiaxed ufg structure, with a large fraction of high angle boundaries (HABs, ∼70%), can be obtained in Zr after only two ARB cycles. The average grain size, counting only HABs (θ > 15°), is 400 nm. (Sub)grain size is equal to 320 nm. The yield stress and UTS values are nearly double those from conventionally processed Zr with only a slight loss of ductility. Optimum processing conditions include large thickness reductions per pass (ε ∼ 75%), which enhance grain refinement, and a rolling temperature (T ∼ 0.3T_m) at which a sufficient number of slip modes are activated, with an absence of significant grain growth. Grain refinement takes place by geometrical thinning and grain subdivision by the formation of geometrically necessary boundaries. The formation of equiaxed grains by geometric dynamic recrystallization is facilitated by enhanced diffusion due to adiabatic heating.