The two-step positive temperature coefficient in resistance characteristics of n-(Ba,Pb)TiO3 ceramics created through inclusion of grain boundary modifier additives

Donor-doped n-(Ba,Pb)TiO3 polycrystalline ceramics exhibit distinctly two-step positive temperature coefficient of resistance (PTCR) characteristics when formulated with suitable combinations of B2O3 and Al2O3 as grain boundary modifiers by heterogeneous addition. B2O3 or Al2O3 when added singularly resulted in either steep or broad PTCR jumps respectively across the phase transition. The two-step PTCR is attributed to the activation of the acceptor states, created through B2O3 and Al2O3, for various temperature regimes above the Curie point (T-c). The changing pattern of trap states is evident from the presence of Ti4+-O--Al3+ type hole centres in the grain boundary layer regions, identified in the electron paramagnetic resonance (EPR) spectra. That charge redistribution occurs among the inter-band gap defect states on crossing the Curie temperature is substantiated by the temperature coefficient in the EPR results. Capacitance-voltage results clearly show that there is an increase in the density of trap states with the addition of B2O3 and Al2O3. The spread in energy values of these trap states is evident from the large change in barrier height (phi similar or equal to 0.25-0.6 eV) between 500 and 650 K.

Suppression of grain boundary relaxation in Zr-doped BiFeO3 thin films

Here, we present the results of temperature dependent dielectric studies on chemical solution processed Zr-doped BiFeO3 (BFO) thin films deposited on Pt/Si substrates. We find that in contrast to the undoped BFO films, Zr doping at Fe-site suppresses the low frequency dielectric relaxation originating from the grain boundaries, attributed to the increased dipolar rigidity due to stronger Zr-O bonds. Temperature dependent dc conductivity obtained from impedance and modulus analyses shows two distinct conduction processes occurring inside the grains. At temperature below similar to 423K, conductivity is nearly temperature independent, while in the high temperature regime (above similar to 423K), conduction is governed by the long range movement of oxygen vacancies with an activation energy of similar to 1eV. (C) 2014 AIP Publishing LLC.

Grain boundary interface mechanics in strain gradient crystal plasticity

Interactions between dislocations and grain boundaries play an important role in the plastic deformation of polycrystalline metals. Capturing accurately the behaviour of these internal interfaces is particularly important for applications where the relative grain boundary fraction is significant, such as ultra fine-grained metals, thin films and microdevices. Incorporating these micro-scale interactions (which are sensitive to a number of dislocation, interface and crystallographic parameters) within a macro-scale crystal plasticity model poses a challenge. The innovative features in the present paper include (i) the formulation of a thermodynamically consistent grain boundary interface model within a microstructurally motivated strain gradient crystal plasticity framework, (ii) the presence of intra-grain slip system coupling through a microstructurally derived internal stress, (iii) the incorporation of inter-grain slip system coupling via an interface energy accounting for both the magnitude and direction of contributions to the residual defect from all slip systems in the two neighbouring grains, and (iv) the numerical implementation of the grain boundary model to directly investigate the influence of the interface constitutive parameters on plastic deformation. The model problem of a bicrystal deforming in plane strain is analysed. The influence of dissipative and energetic interface hardening, grain misorientation, asymmetry in the grain orientations and the grain size are systematically investigated. In each case, the crystal response is compared with reference calculations with grain boundaries that are either 'microhard' (impenetrable to dislocations) or 'microfree' (an infinite dislocation sink). © 2013 Elsevier Ltd. All rights reserved.

Effects of Pr dopant on grain boundary and electrical properties of Ce5.2Sm0.8MoO15-delta

Material formulated as Ce5.2Sm0.8-xPrxMo15-(delta) (x=0.08) was prepared by adding small amounts of Pr dopant in oxide Ce5.2SM0.8-xPrxMoO15-delta. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM) and AC impedance spectroscopy. The effect of small amounts of Pr on microstructure and electrical conductivity was discussed. It was showed that the material doped with Pr has a lot of dents and small openings, which provide channels for oxygen ions, resulting in lower grain boundary and total conductivity activation energy. Thus the corresponding grain boundary conductivity and total conductivity of the material were improved notably. The grain boundary conductivity of the material doped with Pr is 6.79 X 10(-3) S center dot cm(-1) at 500 degrees C, which is twice as large as that without Pr (5.61 X 10(-5) S center dot cm(-1)).

Grain-boundary segregation and precipitates in La2O3 and Pr2O3 doped SnO2 center dot CoO-based varistors

Structural heterogeneities in SnO2.CoO-based varistors were analyzed by transmission electron microscopy. In SnO2.CoO-based system doped with La2O3 and Pr2O3 two kinds of precipitate phases at grain boundary region were found. Using energy dispersive spectrometry they were found to be Co2SnO4 and Pr2Sn2O7, presenting a defined crystalline structure. It was also identified that such precipitate phases are mainly located in triple-junctions of the microstructure. HRTEM analysis revealed the existence of other two types of junctions, one as being homo-junctions of SnO2 grains and other due to twin grain boundaries inside the SnO2.CoO grain. The role of these types of junction in the overall nonlinear electrical features is also discussed. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Ferroelectric state analysis in grain boundary of Na0.85Li0.15NbO3 ceramic

The electric and dielectric properties of the grain boundary of Na0.85Li0.15NbO3 lead-free ferroelectric-semiconductor perovskite were investigated. The impedance spectroscopy was carried out as a function of a thermal cycle. The sodium lithium niobate was synthesized by a chemical route based on the evaporation method. Dense ceramic, relative density of 97%, was prepared at 1423 K for 2 h in air atmosphere. ac measurements were carried out in the frequency range of 5 Hz-13 MHz and from 673 to 1023 K. Theoretical adjust of the impedance data was performed to deriving the electric parameters of the grain boundary. The electric conductivity follows the Arrhenius law, with activation energy values equal to 1.55 and 1.54 eV for heating and cooling cycle, respectively. The nonferroelectric state of the grain boundary and its correlation with symmetry are discussed in the temperature domain. (C) 2003 American Institute of Physics.

Microstructure of an artificial grain boundary weak link in an YBa2Cu3O(7-δ) thin film grown on a (100)(110), [001]-tilt Y-ZrO2 bicrystal

The microstructure of an artificial grain boundary in an YBa2Cu3O7-δ (YBCO) thin film grown on a (100)(110), [001]-tilt yttria-stabilized-zirconia (YSZ) bicrystal substrate has been studied using transmission electron microscopy (TEM). The orientation relationship between the YBCO film and the YSZ substrate was [001]YBCO∥[001]YSZ and [110]YBCO∥[100]YSZ for each half of the bicrystal film. However, the exact boundary geometry of the bicrystal substrate was not transferred to the film. The substrate boundary was straight while the film boundary was wavy. In several cases there was bending of the lattice confined within a distance of a few basal-plane lattice spacings from the boundary plane and microfaceting. No intergranular secondary phase was observed but about 25% of the boundary was covered by c-axis-tilted YBCO grains and a-axis-oriented grains, both of which were typically adjacent to CuO grains or surrounded by a thin Cu-rich amorphous layer.

Properties of artificial grain boundary weak links grown on Y-ZrO 2 bicrystals

Weak links were fabricated by pulsed laser deposition of YBa 2Cu3Ox thin films on Y-ZrO2 bicrystal substrates. They were formed by transferring the bicrystal boundary into the epitaxial film during the film growth. Their properties were determined by the misorientation angle ( theta ) between the two halves of the bicrystal. The transport properties of the weak links were studied as a function of theta and an exponential dependence of the weak link critical current density was observed for angles up to 45 degrees . Clear Josephson effects with good microwave and magnetic field response were observed.

Artificial grain boundary Josephson junctions : properties and applications

Engineered grain boundary Josephson junctions in YBaCuO were formed on bicrystal Y-ZrO2 substrates. Laser deposited films were patterned into micron size microbridges. The authors obsd. a pronounced correlation between superconducting transport properties of grain boundary junctions and the misorientation angle θ between the two halves of the bicrystal. The crit. Josephson current Ic decreased about four orders of magnitude as θ was increased from 0 to 45 degrees. Clear microwave and magnetic field responses were obsd. at 77 K. At this temp., crit. current times normal resistance products, IcRn, of up to 1 mV were measured for low angle grain boundaries, and Shapiro steps were obsd. up to that voltage. DC SQUIDs were fabricated, and best performance at 77 K was obtained for θ = 32° with a 4-μm strip width. To utilize the higher IcRn value of a lower θ, submicron junctions have to be developed. [on SciFinder(R)]

Grain boundary strengthening in strongly textured magnesium produced by hot rolling

The grain size dependence of the yield stress in hot rolled 99.87 pct magnesium sheets and rods was measured in the temperature range 77 K to 420 K. Hot rolling produced strong basal textures and, for a given grain size, the hot rolled material has a higher strength than extruded material. The yield strength-grain size relation in the above temperature range follows the Hall-Petch equation, and the temperature dependencies of the Hall-Petch constants σ0 and k are in support of the theory of Armstrong for hcp metals that the intercept σ0 is related to the critical resolved shear stress (CRSS) for basal slip (easy slip) and the slope k is related to the CRSS for prismatic slip (difficult slip) occurring near the grain boundaries. In the hot rolled magnesium, σ0 is larger and k is smaller than in extruded material, observations which are shown to result from strong unfavorable basal and favorable 1010 textures, respectively. Texture affects the Hall-Petch constants through its effect on the orientation factors relating them to the CRSS for the individual slip systems controlling them.

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.

EPR studies on donor doped BaTiO3 grain boundary layer ceramic dielectrics

Donor doped BaTiO3 ceramics become insulating5 under controlled conditions with effective dielectric constants >10. The changes in EPR signals indicate that a certain fraction of the donor doped BaTiO3 is cubic even at room temperature and that the cubic fraction increases with the donor content. X-ray powder diffraction data support the EPR results. The coexistence of both the phases over a range of temperature is characteristic of diffused phase transition. The effect of grain size variation on EPR signal intensities indicate that the boundary layers surrounding the grains may constitute the cubic phase as a result of higher Ba-vacancies and donor contents at the grain boundary layer than in the bulk. Since the acceptor states arising from the Ba-vacancies and the impurities are activated in the cubic phase, they capture electrons from the conduction band, rendering the cubic phase electrically more insulating than the semiconductive tetragonal grain interiors. Thus, the cubic grain boundary layers act as effective dielectric media where the field tends to concentrate.

Evolution of Grain-Boundary Microstructure and Texture in Interstitial-Free Steel Processed by Equal-Channel Angular Extrusion

The equal-channel angular extrusion (ECAE) of Ti-bearing interstitial-free (IF) steel was performed following two different routes, up to four passes, at a temperature of 300 degrees C. The ECAE led to a grain refinement to submicron size. After the second pass, the grain size attained saturation thereafter. The microstructural analysis indicated the presence of coincident-site lattice (CSL) boundaries in significant fraction, in addition to a high volume fraction of high-angle random boundaries and some low-angle boundaries after the deformation. Among the special boundaries, Sigma 3 and Sigma 13 were the most prominent ones and their fraction depended on the processing route followed. A deviation in the misorientation angle distribution from the Mackenzie distribution was noticed. The crystallographic texture after the first pass resembled that of simple shear, with the {112}, {110}, and {123} aligned to the macroscopic shear plane.

Lowering grain boundary resistance of BaZr0.8Y0.2O3−δ with LiNO3 sintering-aid improves proton conductivity for fuel cell operation

A novel sintering additive based on LiNO3 was used to overcome the drawbacks of poor sinterability and low grain boundary conductivity in BaZr0.8Y0.2O3-δ (BZY20) protonic conductors. The Li-additive totally evaporated during the sintering process at 1600°C for 6 h, which led to highly dense BZY20 pellets (96.5% of the theoretical value). The proton conductivity values of BZY20 with Li sintering-aid were significantly larger than the values reported for BZY sintered with other metal oxides, due to the fast proton transport in the "clean" grain boundaries and grain interior. The total conductivity of BZY20-Li in wet Ar was 4.45 × 10-3 S cm-1 at 600°C. Based on the improved sinterability, anode-supported fuel cells with 25 μm-thick BZY20-Li electrolyte membranes were fabricated by a co-firing technique. The peak power density obtained at 700°C for a BZY-Ni/BZY20-Li/La0.6Sr0.4Co0.2Fe 0.8O3-δ (LSCF)-BZY cell was 53 mW cm-2, which is significantly larger than the values reported for fuel cells using electrolytes made of BZY sintered with the addition of ZnO and CuO, confirming the advantage of using Li as a sintering aid.