Thermal expansion, gas permeability, and conductivity of Ni-YSZ anodes produced by different techniques

The supported Ni-YSZ (50 wt.% Ni?+?50 wt.% Zr_0.84Y_0.16O_1.92) anodes were produced of powders, obtained by the ceramic method, combustion synthesis, deposition of nickel oxide onto the YSZ ceramics, and deposition of 28 wt.% of nickel oxide onto the 39 wt.% NiO?+?61 wt.% YSZ powders. The influence of the NiO-YSZ powder production technique, the amount of pore former and sintering temperature on the porosity, gas permeability, thermal expansion, and anode conductivity were studied. The porosity of anodes made of powders obtained by the ceramic method is always lower than the porosity of the anodes made of powders produced by combustion synthesis under otherwise equal conditions. The anode electrical conductivity greatly depends on the powder production techniques, while the anode thermal expansion is only slightly influenced by them.     

Sintering studies on Ni–Cu–YSZ SOFC anode cermet processed by mechanical alloying

New 40 vol%[(Cu)–Ni]–YSZ cermet materials processed by mechanical alloying (MA) of the row powders are prepared. The powder compacts are sintered in air, hydrogen and inert (argon) atmospheres at a dilatometer and tubular furnace up to 1,350 °C. Sintering by activated surface concept (SAS) can anticipate and enhance the densification in such powders. Stepwise isothermal dilatometry (SID) sintering kinetics study is performed allowing determining kinetic parameters for Ni–YSZ and Ni–Cu–YSZ pellets. Two-steps sintering processes is indicated while Cu-bearing material features the smallest activation energy for sintering. The allied MA–SAS method is a promising route to prepare SOFC fuel cell anode materials.     

A thermoanalysis of phase transformations and linear shrinkage kinetics of ceramics made from ultrafine plasmochemical ZrO2(Y)–Al2O3 powders

The methods of X-ray diffraction analysis, thermogravimetric analysis, differential scanning calorimetry, and dilatometry are used to study special features of the structural-phase state of the 80 mass% ZrO₂(Y)–20 mass% Al₂O₃ plasmochemical powders (PCPs) and their effects on the sintering of composite ceramics. It is revealed that the ZrO₂(Y)–Al₂O₃ powder composite represents a mechanical mixture containing crystalline tetragonal zirconium dioxide and aluminum oxide nanoparticles, the latter found in an amorphous state and partially included into the ZrO₂(Y) lattice, thus forming metastable solid solutions of variable composition. Heating of the composite powder within the temperature range 740–1,000 °C reveals an exothermal effect associated with decomposition of metastable states of aluminum oxide. This is accompanied by the formation of the corundum-phase nuclei having subcritical dimensions. They achieve the critical sizes at higher temperatures T > 1200 °C, when α-Al₂O₃ is finally crystallized. The shrinkage response of the powder compacts during non-isothermal sintering is measured in a sensitive dilatometer. It is shown that the shrinkage curve consists of several stages that closely correlate with the concurrent structural-phase transformation in the composite ZrO₂(Y)–Al₂O₃ powder mixture. The decisive contribution into shrinkage during non-isothermal sintering of composite comes from the high-temperature stages with the maximum shrinkage rate at the temperatures 1,250 and 1,550 °C. It is found out that the regime of sintering the ultrafine PCPs (T = 1,600 °C, t = 1 h) allows producing composite ceramic materials with a porosity of Q ≈ (5–7) %, microhardness H _v = 12.3 GPa, and crack resistance К _1c = (10–11) MPa m^0.5.     

The influence of different additives and the mode of their addition on the sintering behavior and the properties of semiconducting barium titanate ceramics

The influence of different additives (TiO₂, TiO₂/SiO₂, CaO/TiO₂/SiO₂, 2BaO/TiO₂/2SiO₂) and the mode of their incorporation (spray drying: series 1; mixed-oxide method: series 2) on the sintering behavior and the microstructural and electrical properties of n-doped BaTiO₃ ceramics has been investigated. The incorporation of the additives from their aqueous solution by spray drying produces a homogeneous distribution of the additive in the BaTiO₃ matrix powder by coating the BaTiO₃ particles. This homogeneous distribution significantly lowers the activation energy for the densification process compared with that of the powders of series 2. Dynamic and isothermal dilatometric measurements revealed that the sintering process is considered as a classical solid phase sintering followed by recrystallization of the BaTiO₃ matrix particles by a eutectic melt. The densification process is dominated by sliding processes. These sliding processes are caused by the amorphous layer of the additive and by the defect-rich grain boundary layers of the BaTiO₃ grains generated intermediately by diffusion processes and reactions of the matrix material with the additive forming the secondary phases Ba₂TiSi₂O₈ and Ba₄Ti₁₃O₃₀, respectively. In series 1, ceramics with a homogeneous microstructure and useful electrical properties (e.g. low resistivity at room temperature) were already produced at a sintering temperature of 1280°C (with SiO₂-containing additives) due to the homogeneous distribution of the additive. The ceramics of series 2 sintered at the same temperature could only be obtained in poor quality. At higher sintering temperatures the differences between the two series vanished.     

Realization of Low Temperature Densification of Nickelate Ceramics for MLCC Application

We report an improved method for the preparation of highly dense nickelate ceramics at relatively low temperature. It is found that the introduction of appropriate additives during the ball-milling process facilitates the formation of nickelate phase through solid state reaction. Moreover, although high-purity nickelate powders can only be obtained by calcining the mixture of starting materials at temperature higher than 1100 oC. The adoption of powders calcined at 1000 oC, rather than those calcined at higher temperature, is conductive to the low-temperature densification of nickelate ceramics, which is attributed to the small and dispersive particles, and the solid state reaction of the residual starting materials during sintering. Compared with the conventional process, the improved method can reduce the sintering temperature of nickelate ceramics by about 100 oC and decrease the grain size of the obtained ceramics, and therefore makes nickelate meet the fabrication requirements of multi-layer ceramic capacitors(MLCC).     

Nanosized bismuth titanate (Bi4Ti3O12) system drive through auto-combustion process by using suspension titania (TiO2)

Bismuth titanate (Bi₄Ti₃O₁₂) was developed by means of titanium oxide (TiO₂) suspension in auto-combustion process at 220 °C to get nanosized (20 ± 5 nm) bismuth titanate (Bi₄Ti₃O₁₂) powder. Complete piezoelectric phase (tetragonal) was obtained after calcination at 700 °C. Dilatometery of compacts was performed to find out sintering temperature. On the basis of shrinkage results, compacts were sintered at 750, 800, and 850 °C for 2 h. After sintering single phase was obtained with orthorhombic structure analyzed by X-ray diffraction and also investigated by Rietveld method. High-resolution scanning electron microscopy revealed that fine plate-like structure which is a characteristic of BIT powder can be obtained at 850 °C. Sintering results indicate that density and average grain size increase with the increasing temperature. A maximum of about 90 % of the theoretical density was achieved for the sintered product at 850 °C.     

Kinetics of densification of powder compacts during the initial stage of sintering with constant rates of heating. A thermal analysis approach. Part I. Theoretical considerations

Densification of powder compacts during sintering (initial stage) under constant heating rate has been studied and methods of analysing the densification kinetic data have been suggested. p]Green compacts can broadly be envisaged to consists of two phases, viz. porosity and solid material. Annihilation of the pores causes densification of the compacts during sintering. So, the kinetics of the initial stage of densification may very well be represented by a densification parameter (α),where

Here, v_s and v_p,respectively, denote the pore volumes of the sintered and the green compact. Continuous and in situ recording of the linear shrinkage (ΔL) of the compacts during the sintering may be done with a dilatometer and using this value of ΔL,the value of α at any temperature (T) may be calculated.These kinetic data (α vs. T)may then be subjected to analysis using the well-known methods of thermal analysis, and the so-called “derived activation energy (E)” of densification may be evaluated therefrom. The exact form of g(α)—governing rate equation—is ascertained by a trial-and-error method.These methods were used to analyse the densification kinetic data of haematite, copper and silver powders (with particles of irregular shapes and sizes). The results of such analyses will appear on other parts of this paper.     

Kinetics of isothermal oxidation of WC–20Co hot-pressed compacts in air

The present paper presents an isothermal analysis of the oxidation behavior in which hot-pressed compacts rather than powders are used over the temperature range 700–850 °C. This was done to better simulate the extent of oxidation occurring on use. WC–Co powders were first subjected to non-isothermal kinetic analysis to follow the oxidation mechanism. In the isothermal runs, a thermobalance was used to follow up the mass with time at different constant temperatures. The diameter of compacts was measured as function of time at these temperatures, and a simple model was proposed to relate the diameters to extent of oxidation. Two reactions were found to take place that are controlled by chemical reaction at interface: Oxidation of cobalt and oxidation of WC with the formation of WO₃ and CoWO₄. The activation energies for the two steps of oxidation were calculated and found to equal 157 kJ mol^?1 and 205 kJ mol^?1, respectively. These values are in reasonable agreement with published data for WC–Co powders.     

Preparation process of a highly resistant wollastonite bioceramics using local raw materials

Wollastonite (CaSiO₃) is mainly used for traditional ceramics. In this study, wollastonite-based ceramics was obtained by solid state reaction. The starting powders were sintered at different temperatures (850–1,250 °C) for 2 h. Moreover, different amounts of B₂O₃ (0.5–5.0 mass%) have been added. A relative density of about 97% of the theoretical was reached for samples sintered at 1,050 °C for 2 h, containing 3 and 5 mass% B₂O₃. Excellent values of both three point flexural strength (343 ± 34 MPa) and micro-hardness (4.8 GPa) for samples containing 5 mass% B₂O₃, sintered at 1,050 °C for 2 h. Besides this, a relatively low mass loss ratio has been measured (1.1%) for wollastonite samples containing 5 mass% B₂O₃, sintered under the same conditions, after soaking in lactic acid for 9 days. Finally, the bioactivity of wollastonite by the possibility of formation of apatite on the surface of wollastonite immersed in simulated body fluid was confirmed.     

Ageing of wet-synthesized oxide powders

Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original sintering properties can be recovered after washing the aged powders with ethanol in a basic medium.     

Investigation of the Sintering Mechanisms for (U,Am)O2 Pellets Obtained by CRMP Process

The use of CRMP (Calcined Resin Microsphere Pelletization) process for AmBB (Americium Bearing Blankets) fabrication is today a key research axis in americium transmutation domain, where its very high activity requires minimization of powder dissemination. In this aim, the use of oxide microspheres as compaction precursors is a promising clean alternative to powder metallurgy. Understanding the different steps of densification during CRMP pellet sintering thus appears as fundamental to obtain final materials with the specific features required for AmBB. The densification curve recorded in dynamic conditions shows different sintering steps. A first decrease of shrinkage rate happens at low temperature, around 1100 K. This phenomenon is not normally observed in the sintering of conventional powders. Chemical and microstructural studies were performed on (U,Am)O₂ and also on (Ce,Gd)O₂ surrogate compound to highlight the causes of this low-temperature sintering step. Multiscale reorganization finally appears as the sole explanation, through the sintering of nanometric aggregate present in the green pellet and related to the morphology of the starting microspheres employed as pelletization precursors.     

Investigation of sintering behavior of ZrO<Subscript>2</Subscript> (Y) ceramic green body by means of non-isothermal dilatometry and thermokinetic analysis

Using the method of dilatometry, kinetic characteristics of compacts shrinkage manufactured from ultrafine plasmochemical ZrO₂ (Y) powders and commercial Tosoh’s powders are investigated. The shrinkage curves are constructed with a DIL 402 C high-sensitivity dilatometer in a non-isothermal heating mode at different heating rates (1, 2, 5 and 10 °C min^?1). It is shown that the plasmochemical powders are characterized by a lower sintering efficiency than the Tosoh’s powders. The kinetic results are processed using a Netzsch Thermokinetics license software program developed for those who make use of devices manufactured by the Netzsch-Geratebau GmbH. The kinetic characteristics of compact shrinkage are determined as a function of partial length variation using Friedman’s analysis. Considerable differences are found between the values of apparent shrinkage activation energy for plasmochemical and Tosoh’s powders in the initial and final shrinkage stages. We attribute the mentioned differences in phase composition of the powders and their degree of agglomeration. In the intermediate shrinkage stage, the values of the apparent activation energy obtained for both types of powders have only marginal differences.     

TiC nanocrystal formation from carburization of laser-grown Ti/O/C nanopowders for nanostructured ceramics

Refractory carbide ceramics (TiC and ZrC) raise interest as promising materials for high-temperature applications such as structural materials for the future generation of nuclear reactors. In this context, nanostructured ceramics are expected to exhibit improved thermomechanical properties as well as better behavior under irradiation when compared to conventional materials. It is therefore necessary to synthesize carbide nanocrystals of such materials to elaborate the ceramics. We report here the formation study of TiC nanocrystals through the direct carburization of Ti/O/C nanopowders grown by laser pyrolysis. A spray of titanium tetraisopropoxide was laser pyrolyzed with ethylene as the sensitizer, leading to Ti/O/C nanopowders with various C contents controlled by the synthesis conditions. Annealing treatments performed on these nanopowders under an inert atmosphere without any C addition enabled the formation of TiC grains through the carburization of the oxide phase by free C incorporated during the synthesis. The powders were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The final TiC grain size was about 80 nm, and the grains were monocrystalline. The influence of the free C content on the grain growth during the annealing step, together with its effects on the densification of the ceramics after sintering by high-pressure flash sintering, was examined. A 93% densification was finally achieved.     

Magnetic Investigation of Various NiFe<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>4</Subscript> Ferrite Nanostructures Synthesized by Ball Milling Technique

NiFe_2?x Bi _x O₄ (x = 0, 0.1, 0.2, 0.3) nanoparticles with various grain sizes were synthesized via annealing treatment followed by ball milling of its bulk component materials. Commercially available bismuth, nickel and iron oxide powders were first mixed and then annealed at 1200 °C in an oxygen environment furnace for 4 h. The samples were then milled for 2 h by high-energy ball milling. X-ray diffraction (XRD) pattern indicated that in this stage the samples are single phase. The microstructure investigation was carried out by a scanning electron microscope with maximum magnification of 30,000. The average grain size for different samples was estimated by XRD technique and transmission electron microscopy. Magnetic behavior of the samples at room temperature was studied using an alternating gradient force magnetometry. The Néel temperature of the powders was measured by a Faraday balance. Based on magnetic studies, increase in bismuth content leads to a decrease in the saturation magnetization, coercive field and Néel temperature. This can be attributed to the substitution of Bi³⁺ ion in the ferrite system as a nonmagnetic cation.     

Porosity of shapes from hydrothermally treated titania

Titania nanopovvders obtained by hydrolysis of titanium alkoxides and consecutive hydrothermal treatment were compacted and sintered. The influence of preparation conditions (alkyl, pH of hydrolysis, temperature of hydrothermal treatment, compacting pressure, sintering temperature) on the porosity of powders, compacts and sintered bodies was investigated by nitrogen sorption and mercury intrusion. Optimum conditions are derived to prepare high-density ceramics at relatively low sintering temperature.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

A role of BNLT compound addition on structure and properties of PZT ceramics

In this research, effects of lead-free bismuth sodium lanthanum titanate (BNLT) addition on structure and properties of lead zirconate titanate (PZT) ceramics were investigated. PZT ceramics with addition of 0.1–3.0 wt%BNLT were fabricated by a solid-state mixed oxide method and sintering at 1050–1200 °C for 2 h to obtain dense ceramics with at least 96% of theoretical density. X-ray diffraction indicated that complete solid solution occurred for all compositions. Phase identification showed both tetragonal and rhombohedral perovskite structure of PZT with no BNLT phase detected. Scanning electron micrographs of fractured PZT/BNLT ceramics showed equiaxed grain shape with both transgranular and intergranular fracture modes. Addition of BNLT was also found to reduce densification and effectively limited grain growth of PZT ceramic. Optimum Hv and K_IC values were found to be 4.85 GPa and 1.56 MPa.m^1/2 for PZT/0.5 wt%BNLT sample. Among PZT/BNLT samples, room temperature dielectric constant seemed to be improved with increasing BNLT content. The maximum piezoelectric coefficient values were observed in pure PZT ceramic and were slightly decreased in BNLT-added samples. Small reduction of remanent polarization and coercive field in hysteresis loops was observed in BNLT-added samples, indicating a slightly suppressed ferroelectric interaction in this material system.     

Vacuum balance studies of phosphate-bonded oxide ceramics

Methods of phosphate bonding of oxide ceramics are summarised. Applications of vacuum balance techniques are described to study the sintering of lime, magnesia, alumina and kaolin in the presence of phosphoric acid and sodium polymetaphosphate additives. Changes in surface area, crystallite and aggregate sizes during sintering have been determined by gravimetric B.E.T. nitrogen gas sorption techniques, supported by X-ray diffractometry, optical and electronmicroscopy.Phosphoric acid has comparatively little influence on lime and magnesia sintering. There is no enhancement of sintering and even slight activation at temperatures between 800–1000 °C, when chemical reactions with the additive are completed. In contrast, sodium polymetaphosphate additive enhances sintering of lime and magnesia at temperatures between 500–1000 °C. When kaolin is calcined with sodium polymetaphosphate, the activated alumina in the intermediate metakaolinite readily forms aluminium phosphate to accelerate sintering.     

Diol—Based Sol–Gel as a Novel Binder for Barium Titanate Ceramics

The relative merits of using a diol-based sol–gel precursor as a binder in the fabrication of barium titanate ceramics made by die-pressing a mixed oxide starting powder have been investigated. The characteristics of powder compacts were compared to samples prepared using a conventional PVB organic binder. The green strength of pellets with the PVB binder was higher than for samples containing the gel, but strength after binder burnout from gel samples was double that of pellets made with PVB. The gel led to improvements in densification during sintering, but these were most noticeable at low sintering temperatures and at intermediate stages of densification. After sintering for 2 h at 1150C, the gel-containing samples reached 75% of theoretical density, some 5% more than for the organic polymer binder. Sintering at 1300C for 2 h, gave a sintered density of ~96% of theoretical density using the gel additive, which was only 2% higher than for the conventional PVB binder system. The decomposition characteristics of the gel were investigated by TGA, FTIR and GC-MS techniques.     

Aging of electrolyte La0.88Sr0.12Ga0.82Mg0.18O3 − δ made using magnetic-pulse compaction

Ceramics of the La_0.88Sr_0.12Ga_0.82Mg_0.18O_{3 ? δ} solid electrolyte was obtained by magnetic-pulse compaction (MPC) of a powder synthesized using the self-propagating high-temperature synthesis technique with further sintering at 1380°C. Conductivity and its change in time were studied. It was shown that conductivity of fresh samples coincides with conductivity of ceramics obtained using the classical solid-phase synthesis. It was established that conductivity of electrolyte decreased by 18% during isothermal exposure at 700°C for 1 year.     

Comparison of the effect of <Emphasis Type="Italic">Pleurotus citrinopileatus</Emphasis> extract and vitamin E on the stabilization properties of camellia oil

We selected Camellia tenuifolia (Hayata) seed oil to compare the effects of mushroom extract and vitamin E on its stabilization properties. Camellia tenuifolia was selected for its higher oil content, but its proportions of unsaturated fatty acids and natural antioxidants as well as its oxidation stability are lower than those of Camellia oleifera oil. Our aim was to improve the oxidation stability, thermal stability, and photodegradation of C. tenuifolia seed oil and then compare the advantages of mixing traditional antioxidant (vitamin E) and mushroom natural antioxidant components (mushroom extract) in the oil. The focus was on the analysis of the effects of Pleurotus citrinopileatus (Singer) extract and vitamin E on the stabilization properties of C. tenuifolia seed oil, which involved some degradation research, such as evaluating the thermal, oxidation, and antioxidant effects as well as the irradiative (pulsed light) stability of the original oil and oil mixed with additives for comparing the differences by differential scanning calorimetry tests and isothermal microcalorimeter (TAM Air) analyses. We determined the effects of stabilization additives vitamin E and various PC extract doses by using pulsed light irradiation (0, 30, and 60 pulses) and found that the 3 mass% PC extract had the best antiphotodegradation characteristics, and the 0.1 mass% vitamin E indicated the outstanding oxidation stability for among all of the additives in this study. Overall, we obtained the following suitable conditions to stabilize camellia oil: addition of vitamin E, addition of 3 mass% PC extract, and a nitrogen atmosphere.