Microstructure,conductivity and mechanical properties of calcia stabilized zirconia ceramics obtained from nanosized precursor and reduced graphene oxide doped precursor powders

In the work 12CaO-88ZrO₂ (12CSZ, mol%) ceramics was manufactured both from nanopowder, obtained via cryochemical technique, and composite precursor 12CSZ?+?0.25?wt% rGO (reduced graphene oxide). Via SEM, XRD and Raman spectroscopy the detailed investigation of the effect of the precursor type and intermediate processing on the microstructure and electrical conductivity of ceramics was carried out. It was shown that rGO is completely removed during the annealing at 1550?°C for 3?h in air with no effect on the high ionic conductivity of ceramics. The use of nanosized powder and the additional processing step results in vacuum dense solid electrolytes characterized by well-formed cubic zirconia based solid solution, thin discontinuous grain boundaries and rather high ionic conductivity. The addition of rGO leads to slight microhardness (HV) decrease comparing to ceramics manufactured from the nanosized precursor. As a result, a new technique for zirconia based solid electrolytes having both high electrical conductivity at high temperatures and sufficient mechanical properties was suggested.     

Improvement in fracture strength in electrically conductive AlN ceramics with high thermal conductivity

It is possible to impart electrical conductivity to insulating aluminum nitride (AlN) ceramics by precipitating a yttrium oxycarbide grain boundary phase with electrical conductivity. However, previously, sintering at high temperature was required to increase the electrical conductivity through the transformation of the grain boundary phase from yttrium aluminum oxide (Al₂Y₄O₉) to rare-earth oxycarbide. As a result, the increase in electrical conductivity was accompanied with a considerable decrease in the fracture strength due to grain growth of AlN. In this study, sintering temperature and additive compositions were investigated to maintain the high strength of electrically conductive AlN without losing the high thermal conductivity.     

High-current measurement of the grain resistivity in zinc oxide varistor ceramics

A new pulse technique for grain resistivity measurement in varistor ceramics is suggested. Such technique allows obtaining more precise value of the grain resistivity due to the use of the concept of differential electrical resistance. This technique can be used in the current density range where the overheating of varistor sample is insignificant. The technique was verified using commercial ZnO varistors. Grain resistivities of 0.60±0.02 Ω cm at 293 K and of 3.40±0.13 Ω cm at 77 K were obtained. This result indicates the negative temperature coefficient of grain resistance in ZnO varistor in the range (77–293) K. The contribution of the grain boundaries to the current–voltage characteristic of ZnO varistor is estimated on the basis of the measured grain resistivity and the current–voltage data. It is shown that the electrical conduction in ZnO varistor is controlled by grains if the current density exceeds approximately 1000 А сm⁻².     

Effects of microstructure and intergranular glassy phases on thermal conductivity of silicon nitride

In this study, the binary sintering additives Y₂O₃-Sc₂O₃, were first applied to the Si₃N₄ system to investigate their effects on microstructure and thermal conductivity. The microstructure and thermal conductivity of both sintered silicon nitride (SSN) and sintered reaction-bonded silicon nitride (SRBSN) were found to be significantly dependent on the additive composition. Among various combinations of Y₂O₃ and Sc₂O₃, 1 mol% Y₂O₃−3 mol% Sc₂O₃ prominently enhanced thermal conductivity, and the enhancement could not be attributed to any difference in microstructure or lattice defects. TEM observation revealed that this composition was more liable to devitrify the glassy phase with a lower degree of stress accumulation, and to possibly produce a grain boundary that was cleaner or with a higher order of atomic arrangement. A microstructure model for thermal conductivity was proposed which took the thermal resistance of the grain boundaries into account. The grain boundary state exerted a remarkable influence on the thermal conductivity of fine microstructures, and the experimentally measured thermal conductivity values were consistent with those given by the proposed model.     

Preparation of dense La0.7Ca0.3MnO3 ceramics from freeze-dried precursors

Sinterability of La_0.7Ca_0.3MnO₃ precursors, obtained by the freeze-drying method, is studied in order to develop a technique for preparation of dense (>95%) ceramics for CMR measurements and sputtering applications. Single phase powders, obtained by thermal decomposition at 650°C, were subjected to deagglomeration by ultrasonic or mechanical treatment. Sintering of deagglomerated powders for several hours at T=1200–1300°C allowed to achieve densities up to 97–98%. The best sinterability is demonstrated by mechanically processed powder, but further sintering of ceramics, obtained from this precursor, results in significant dedensification (up to 85% at 1300°C). Analysis of precursors and dedensified samples shows at high temperature decomposition of carbonates in closed pores to be the most probable reason for the observed process.     

Fabrication of YAG transparent ceramics by two-step sintering

Yttrium aluminum garnet (YAG) nanopowders with mean particle size of about 50 nm synthesized by a modified co-precipitation method were used to sinter bulk YAG ceramic by two-step sintering method. Full densification was achieved by heating the sample up to 1800 °C followed by holding at 1550 °C for 10 h. Transparent YAG ceramics were obtained by suppressing grain-boundary migration while promoting grain-boundary diffusion during the two-step sintering process. The microstructure of the YAG ceramic is homogeneous without abnormal grain growth and the transmittance of the sintered sample is 43%.     

Effect of oxygen treatment on structure and electrical properties of Mn-doped Ca0.6Sr0.4TiO3 ceramics

Different oxygen treatment methods, including O₂ and N₂ annealing, were conducted on Ca_0.6Sr_0.4TiO₃ (CST) ceramics with varying Mn content (0?mol%, 0.5?mol% and 2.0?mol%). Structure characterization, including XRD and SEM, indicated the minimal effect of annealing on the microstructure. Grain boundaries were found to be sensitive to oxygen treatments, and annealing in O₂ resulted in increased grain boundary resistance, while in N₂ led to the opposite result. The insulating properties of bulk ceramics were found to be dominated by grain boundaries. Both the concentration and mobility of oxygen vacancies were confirmed to affect the energy storage properties to some extent in this work.     

Electrical properties and structure of grain boundaries in n-conducting BaTiO3 ceramics

The electrical properties of positive temperature coefficient (PTC) ceramics are expected to strongly correlate with the potential barrier height at grain boundaries, which in turn may be influenced by the grain boundary structure and chemistry. In this study, n-conducting BaTiO₃ ceramics co-doped by La and Mn were prepared, and the electrical properties were determined by impedance spectroscopy and dc four-point van der Pauw measurements. Detailed analysis of the grain boundary structure was performed by electron microscopy techniques across different length scales. The study revealed that the randomly oriented polycrystalline microstructure was dominated by large angle grain boundaries, which in the present case were dry although a secondary crystalline and glass phase formed at triple junctions. The relationship between the observed grain boundary atomic structures and electrical properties is briefly discussed.     

Conductivity of porous materials with spheroidal pores

Models predicting the conductivity of porous materials with spheroidal insulating pores are summarized and a new model, based on our exponential relation, is proposed. Using the well-known single-inclusion solution for spheroids, Maxwell coefficients (“intrinsic conductivities”) are calculated in dependence of the pore aspect ratio for isotropic microstructures with randomly oriented spheroidal pores, and implemented into the three traditional effective medium approximations (Maxwell-type, self-consistent, differential) and our exponential relation. As expected, all models predict that prolate pore shape has a very small influence on the porosity dependence, while oblate pores affect the porosity dependence of conductivity significantly. However, the self-consistent predictions are linear and imply spurious percolation thresholds, whereas Maxwell-type and differential models (power-law relations) are known to provide predictions that are unrealistically high for the special case of spherical pore shape. Thus, our exponential relation seems to be currently the most suitable relation for implementing the single-inclusion solution for spheroids.     

Thermal and Electrical Conductivity of Amorphous and Graphitized Carbide‐Derived Carbon Monoliths

The influence of graphitization and composition of carbide‐derived carbon (CDC) monoliths on the electrical and thermal conductivity was investigated. Carbon monoliths with varying porosities were synthesized employing biomorphous macroporous TiC and SiC as precursors. Graphitization was carried out in situ during high‐temperature chlorination with and without addition of nickel, iron, and cobalt chloride to the carbide. The graphitized monoliths showed improved properties. The results demonstrate that despite graphitic carbon also glass‐like carbon, stemming from the carbide synthesis, increases the thermal and electrical conductivity significantly.     

Fabrication,microstructure and high-temperature plastic deformation of three-phase Al2O3/Er3Al5O12/ZrO2 sintered ceramics

The fabrication, microstructure and high-temperature creep behavior of chemically compatible, three-phase alumina/erbium aluminum garnet (Er₃Al₅O₁₂, EAG)/erbia fully-stabilized cubic ZrO₂ (ESZ) particulate composites with the ternary eutectic composition is investigated. The composites were fabricated by a solid-state reaction route of α-Al₂O₃, Er₂O₃ and monoclinic ZrO₂ powders. The final phases α-Al₂O₃, EAG and ESZ were obtained after calcination of the powder mixtures at 1400 °C. High dense bulk composites were obtained after sintering at 1500 °C in air for 10 h, with a homogeneous microstructure formed by fine and equiaxed grains of the three phases with average sizes of 1 μm. The composites were tested in compression at temperatures between 1250 and 1450 °C in air at constant load and at constant strain rate. As the temperature increases, a gradual brittle-to-ductile transition was found. Extended steady states of deformation were attained without signs of creep damage in the ductile region, characterized by a stress exponent of nearly 2 and by the lack of dislocation activity and modifications in grain size and shape. The main deformation mechanism in steady state is grain boundary sliding, as found in superplastic metals and ceramics. In the semibrittle region, microcavities developed along grain boundaries; these flaws, however, did not grow and coalescence into macrocracks, resulting in a flaw-tolerant material. Alumina is the creep-controlling phase in the composite because of the grain boundary strengthening caused by the (unavoidable) Er³⁺- and Zr⁴⁺-doping provided by the other two phases.     

Replies to comments contained in “Conductivity hysteresis in polymer electrolytes incorporating poly(tetrahydrofuran)” by O. Akbulut, et al., Electrochim. Acta 52 (2007) 1983

DSC indicates that first-heating endotherms at 95 and 100-115 °C in poly(tetramethylene oxide)-based polymers with LiClO₄ and LiBF₄, respectively, arise from the decomposition of phase-separated LiClO₄·3H₂O and a pre-melting transition in phase-separated LiBF₄ and not from organized adducts with poly(tetramethylene oxide) as asserted by Akbulut et al. and other literature. Water in the LiClO₄ system, at least (absent in freeze-dried samples), could account for higher conductivities reported by Akbulut et al. than observed by the present authors. Irreversibility of log σ versus1/T in these weakly ionophilic systems apparently arises from slow dissolution of lithium salts together with morphological changes in mixtures of the self-organising systems CmOn (I) with the ‘grain boundary bridging’ copolymer -[-(CH₂)₄-O-]_x-(CH₂)₁₂- (II). A three-component system I:II:LiBF₄ to which 9 wt% of tetrahydrofuran had been purposefully added showed deterioration in conductivity compared with the system without THF addition. This suggests that solvent-inhibition of self-organization is contrary to the suggestion by Akbulut et al. that irreversible transformation to a high ambient conductivity (σ = 10⁻⁴ to 10⁻³ S cm⁻¹) regime arises from plasticization by the 3 wt% of volatiles, generated by thermal decomposition of II in a three-component mixture, that they report. The irreversible transformation to higher conductivities is also observed in systems heated to maximum temperatures between 50 and 80 °C for which degradation was shown to be negligible.     

New approach for distribution of carbon nanotubes in alumina matrix

Alumina–carbon nanotubes composites were studied with respect to obtain the homogeneous distribution of nanotubes within the alumina matrix. Disaggregation and uniform dispersion of carbon nanotubes in alumina matrix are crucial requirements for improvement fracture toughness and also electrical conductivity of these composites. New approach comprises functionalisation MWCNTs by acid treatment, stabilisation of alumina/MWCNT dispersion with subsequent freezing has been used, which resulted in formation of granulated homogenous mixture. The ceramic composites were prepared by hot pressing at 1550 °C using these mixtures. Microstructural analysis as well as electrical conductivity measurements has been used for observation of distribution of nanotubes within composites. Electrical conductivity, as an indicator of homogeneity of conductive network distribution, increases from 6 to 1140 S/m when compared the conventional process and approach presented in this work at the same volume fraction of MWCNTs 10 vol.%.     

Synthesis, densification and electrical properties of strontium cerate ceramics

Powders of pure and 5% ytterbium substituted strontium cerate (SrCeO₃/SrCe_0.95Yb_0.05O_3−δ) were prepared by spray pyrolysis of nitrate salt solutions. The powders were single phase after calcination in nitrogen atmosphere at 1100 °C (SrCeO₃) and 1200 °C (SrCe_0.95Yb_0.05O_3−δ). Dense SrCeO₃ and SrCe_0.95Yb_0.05O_3−δ materials were obtained by sintering at 1350–1400 °C in air. Heat treatment at 850 and 1000 °C, respectively, was necessary prior to sintering to obtain high density. The dense materials had homogenous microstructures with grain size in the range 6–10 μm for SrCeO₃ and 1–2 μm for SrCe_0.95Yb_0.05O_3−δ. The electrical conductivity of SrCe_0.95Yb_0.05O_3−δ was in good agreement with reported data, showing mixed ionic–electronic conduction. The ionic contribution was dominated by protons below 1000 °C and the proton conductivity reached a maximum of 0.005 S/cm above 900 °C. In oxidizing atmosphere the p-type electronic conduction was dominating above 700 °C, while the contribution from n-type electronic conduction only was significant above 1000 °C in reducing atmosphere.     

Synthesis,Characterization and Electrical Conductivity of Polyesters Containing Azomethine Linkages

Abstract

The synthesis and characterization of some polyesters containing azomethine linkages are reported here. The electrical conductivity of these polyesters is measured and the results are explained with simple Pariser-Parr-Pople calculations. The polymers are doped with Ag and the electrical conductivity of most of the doped polymers is found to register significant increase. Attempts are made to explain this increase in electrical conductivity.     

Micro-scale fracture toughness of textured alumina ceramics

Enhanced fracture resistance of textured alumina is ascribed to crack deflection along grain boundaries. In this work, we quantify and compare the micro-scale fracture toughness of textured alumina grains and grain boundaries by micro-bending tests. Notched micro-cantilevers were milled from single alumina textured grains (perpendicular to the [0001] direction) and across several textured grains (along the [0001] direction), using a focused ion beam technique. Bending tests were performed with a nanoindenter. A shape function for notched pentagonal-shaped cantilevers was developed using finite element analysis. The critical stress intensity factor at the notch tip was determined based on the measured fracture loads. The micro-scale fracture toughness of the textured alumina grain boundaries (2.3 ± 0.2 MPa m^1/2) was about 30% lower than that of the grains (3.3 ± 0.2 MPa m^1/2). These findings at the micro-scale are paramount for understanding the macroscopic fracture behaviour of textured alumina ceramics.     

高聚物/炭黑复合材料导电性能的研究

本文介绍了炭黑（ＣＢ）对低密度聚乙烯（ＬＤＰＥ）、高密度聚乙烯（ＨＤＰＥ）、聚苯乙烯（ＰＳ）等高分子材料导电性能的影响,研究了其导电性能和导电机理,分析了不同导电体系中基体对炭黑临界值的影响。     

Correlation between microstructure and electrical conductivity in composite electrolytes containing Gd-doped ceria and Gd-doped barium cerate

Composite electrolytes with nominal compositions, Ce_0.8Gd_0.2O_1.9 + xBaO (x = 0.2 and 0.3), have been synthesized through the citrate route. Formation of two phases, namely Gd-doped ceria and Gd-doped barium cerate, has been confirmed through XRD and SEM studies. The impedance spectra show three distinct semi-circles, all originating from the composite electrolytes. In the temperature range 175-350 °C, the activation energies for the conductivity values extracted from the high frequency and intermediate frequency parts of the impedance spectra remains the same, irrespective of compositional and micro-structural variation. On the other hand, the activation energies for the conductivity values associated with the low frequency impedance spectra show a significant change with micro-structural variation. Solid oxide fuel cells constructed using these composite electrolytes exhibit a higher open circuit voltage compared to those based on single phase 20 mol% Gd-doped ceria.     

Charge trapping characteristics of alumina based ceramics

The space charge dynamics is very important for electrical breakdown of alumina based ceramics. In this paper, the charge trapping/detrapping characteristics of alumina based ceramics were studied by means of isothermal surface potential decay (ISPD) method. For alumina and zirconia toughened alumina (ZTA) ceramic samples, the ISPD curves charged by corona discharge as well as microstructure characterization were carried out. For the first time, crossover phenomenon and hollow shaped potential profile were observed and reported in alumina based ceramics, indicating a surface potential decay process dominated by charge injection and volume conduction affected by the trap states in materials. In addition, the comparative trapping characteristics were evaluated based on a charge detrapping controlled decay model. The correlation between trap distribution and microstructure of alumina based ceramics was investigated. It was proposed that different charge trapping characteristics of alumina based ceramic samples was caused by varied shallow trap density of grain boundary.