Oxygen evolution during the formation and sintering of nickel-manganese oxide spinels for thermistor applications

Nickel-manganese spinel, prepared from 20 wt % NiO and 80 wt % Mn₂O₃, forms at 950°C by the intermediate formation of Mn₃O₄ with evolution of oxygen, determined by mass-spectrometric evolved gas analysis. On heating to higher temperatures, further oxygen is evolved resulting in pore formation and bloating of pressed sintered samples and anomalies in their densification and electrical properties. Thermodynamic considerations and X-ray diffraction intensity measurements suggest that all the Mn²⁺ is located in the tetrahedral spinel sites, this cation configuration remaining unchanged by higher-temperature treatments such as sintering.     

Sintering behaviour of hydroxyapatite reinforced with 20 wt % Al2O3

Hydroxyapatite reinforced with 20 wt% Al₂O₃ was sintered at 1200, 1300 and 1400°C. The sintering behaviour was investigated using X-ray diffraction and electron microscopy. Calcium aluminate phases were observed to be produced by the solid-state reaction between Al₂O₃ and hydroxyapatite. As a hard phase these phases influence the densification of hydroxyapatite with 20 wt% Al₂O₃ due to different sintering rates between the matrix and calcium aluminate.     

Effect of sintering temperature on dielectric properties of Ba0.6Sr0.4TiO3–MgO composite ceramics prepared from fine constituent powders

Composite ceramics of Ba_0.6Sr_0.4TiO₃ + 60 wt.% MgO were prepared from fine constituent powders by sintering at 1200–1280 °C. The composite specimens sintered at the relatively low temperatures showed satisfactory densification due to fine morphology of the constituent powders. The elevation of sintering temperature promoted the incorporation of Mg²⁺ into the lattice of the Ba_0.6Sr_0.4TiO₃ phase and grain growth of the two constituent phases. The dependence of the dielectric properties on sintering temperature was explained in relation to the structural evolution. Controlling the sintering temperature of the composite was found to be important to achieve the desired nonlinear dielectric properties. Sintering at 1230 °C was determined to be preferred for the composite in terms of the nonlinear dielectric properties. The specimen sintered at the temperature attained a tunability of 17.3% and a figure of merit of 127 at 10 kHz and 20 kV/cm.     

Sintering and piezoelectric properties of Pb(Ni1/3Sb2/3)O3-PbZrO3-PbTiO3 ceramics

The sintering and piezoelectric properties of Pb(Ni_1/3Sb_2/3)O₃-PbZrO₃-PbTiO₃ ceramics have been investigated. When the powders contain 48 mol% PbTiO₃ and less than 10 mol% Pb(Ni_1/3Sb_2/3)O₃ followed by calcination at 850°C for 2 h, the calcine only contains the perovskite structure; but if the Pb(Ni_1/3Sb_2/3)O₃ content is between 12 mol% and 14 mol%, both tetragonal and rhombohedral phases are obtained. The composition of the morphotropic phase boundary(MPB) in the Pb(Ni_1/3Sb_2/3)O₃-PbZrO₃-PbTiO₃ system is Pb(Ni_1/3Sb_2/3)O₃ = 12 mol%, PbZrO₃ = 40 mol% and PbTiO₃ = 48 mol%. As the composition at the MPB is sintered at 1260°C and 1280°C for 2 h, respectively, the maximum density (7.8 g/cm³) is obtained. The SEM micrographs indicate that a decrease in porosity with increasing sintering temperature is attained at 1280°C, which is due to a decrease in the number and size of pores. When the sintering temperature is higher than 1280°C, the porosity increases due to PbO evaporation leading to an increase of the number of pore sites and in enlargement of the pore diameter. When the compact composition at MPB is sintered at 1280°C for 2 h, the planar coupling coefficient (K _p) and mechanical quality coefficient (Q _m) tend to approach the maximum (0.488) and minimum values (292.5), respectively.     

Effect of iron particle addition on the pseudocapacitive performance of sol–gel derived manganese oxides film

Manganese oxide electrodes with promising behavior were prepared successfully by sol–gel process. Manganese oxide films were also modified with the addition of submicron-crystalline iron powders. Effects of post heat treatment and iron submicron-powder addition on the material characteristics and electrochemical capacitance of the manganese oxide electrodes were investigated. The experimental results showed that manganese oxide films composed from metal-organic precursors at 250 °C heat treatment, while formation of MnO₂, Mn₂O₃, Mn₃O₄, Fe₂O₃, and Fe₃O₄ phases were observed after heat treatment at a temperature higher than 300 °C. The specific capacitances were 48.9, 140.1, 212.7, and 81.1 F g⁻¹ for manganese oxide films heat treated at 250, 300, 350, and 400 °C, respectively. The specific capacitances were 75.7, 227.3, 247.9, and 152.9 F g⁻¹ for manganese/iron oxide films (Mn:Fe = 100:1) heat treated at 250, 300, 350, and 400 °C, respectively. The manganese/iron oxide films (Mn:Fe = 100:1) treated at 350 °C exhibited the highest specific capacitance 247.9 F g⁻¹ of the electrodes investigated in the present study. After 1000 cyclic voltammetry tests, the specific capacitance decreased by only 10 percent. The surface morphology of this film exhibited powders with linked nano-sized particles. The number of special particles reached a maximum after heat treatment at 350 °C. The experimental results showed that post heat treatment and iron submicron-particle addition may change the surface morphology and structure, increase the specific capacitance, and improve the electrochemical performances of the manganese oxide electrodes.     

Investigation in the sintering of Y2O3 powders in the temperature range 1000 to 1400° C

This paper is devoted to a study of the sintering of two Y₂O₃ powders in the temperature range where only minor densification occurs. Two powders have been examined; one powder, Y₂O₃-A, was obtained by decomposition of hydroxide, because earlier examinations showed [11] that use of this powder resulted in the highest densities of samples in the sintering temperature range from 1300 to 1900° C. The second powder, Y₂O₃-D, was purchased externally. In order to ensure that the pores in the Y₂O₃-A compacts closed as late as possible, the heating rates up to the appropriate temperatures (1000 to 1400° C) were varied in the range 0.013 to 6° C sec^–1. The results obtained show that the heating rate in this temperature range, for the powder obtained by decomposition of hydroxide, is of primary importance in the densification of the material, and that cessation of shrinkage was not observed in the period of 240 min.     

Effect of additive-oxide amount on sintering of Si3N4 with Y2O3 and Nd2O3

The effect of additive amount on the gas-pressure sintering of silicon nitride is investigated. Silicon nitride containing 0.5 to 10 mol % (SN10) of equimolar Y₂O₃-Nd₂O₃ is fired at 1600 to 1900 °C for 4 h in 10 M Pa N₂ gas. A small amount of oxide (1 mol %; SN1) is effective for densification as well as a larger amount of oxide (6–10 mol %) when fired at 1900 °C. Composition analysis of sintered specimens indicates that SN1 densifies through a small amount of SiO₂-rich liquid-phase, whereas SN10 densifies by way of a large amount of additive-oxide-rich liquid phase.     

Investigation of strontium-doped La(Cr,Mn)O3 for solid oxide fuel cells

The (La, Sr) (Cr, Mn)O₃ system was investigated in an effort to develop an interconnect and cathode materials for solid oxide fuel cells. Sintering studies were done in air at temperatures below 1500°C. Significant improvements in densification were observed with substitution of 50 mol% Mn for chromium and a density of 95% theoretical was achieved with the substitution of 70 mol% Mn for chromium in the La(Cr, Mn)O₃ system. Electrical conductivity (d.c.) measurements were made as a function of temperature and oxygen activity. At 1000°C and 1 atm oxygen, the electrical conductivity ranged from 2.2–20 S cm^–1 for LaCr_0.8Mn_0.4O₃ and La_0.9Sr_0.1Cr_0.2Mn_0.8O₃, respectively. All of the compositions showed similar dependence of electrical conductivity on the oxygen activity. Dependence was small at high oxygen activities; as the oxygen activity decreased, a break in electrical conductivity at 10^–12 atm and 1000°C was observed, and then the electrical conductivity decreased asP _O2 ^1/4 . Sintering and electrical conductivity studies indicate that La_0.9Sr_0.1Cr_0.2Mn_0.8O₃ appears to be a candidate for solid oxide fuel cell applications.     

Sintering and compensation effect of donor and acceptor codoped 3 mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350°C. The enhancement is accounted for by a liquid phase sintering mechanism. While the addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol% at 1300–1600°C results in the decrease of final density and in the destabilization of the tetragonal (t) phase of the 3 mol% Y₂O₃-t-ZrO₂ (TZP). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m) ZrO₂ phase and a second Ta₂Zr₆O₁₇ phase. The decrease is attributed to the increase of m-ZrO₂ content in these samples. Complete phase transformation from t-ZrO₂ to m-ZrO₂ observed in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor and acceptor codoping defect chemistry.     

Advances in pressureless densification of boron carbide

The coarsening processes which occur concurrently with the sintering of B₄C were deduced using differential dilatometry, weight loss and grain size measurements. B₂O₃ coatings on B₄C particles stalled the onset of densification until these coatings decomposed away at 1840°C. Oxide gaseous species formed in this process were postulated to be one conduit of particle coarsening. At higher temperatures, the volatilization of B₄C itself were interpreted to be the second vapor phase coarsening mechanism, starting at temperatures above 2000°C. Carbon additions or soaking the compact in a hydrogen-containing atmosphere at 1350°C removed the oxide coatings at temperatures below those in which sintering or coarsening occurred. Accelerating densification above 2130°C was attributed to nonstoichiometric volatilization, leaving carbon behind to facilitate activated sintering.     

Sintering and compensation effect of donor- and acceptor-codoped 3mol% Y2O3-ZrO2

Addition of 0.15–0.5 mol% acceptor oxide, Al₂O₃, to 3 mol% Y₂O₃-ZrO₂ results in enhanced densification at 1350 °C. The enhancement is accounted for by a liquid phase sintering mechanism. The addition of donor oxide, Ta₂O₅, of 0.15–2.5 mol % at 1300–1600 °C results in the destabilization of tetragonal (t-) phase and the decrease of final density in 3 mol% Y₂O₃-TZP (tetragonal ZrO₂ polycrystals). X-ray diffractometry (XRD) reveals that the Ta₂O₅-added 3 mol% Y₂O₃-ZrO₂ contains monoclinic (m-) ZrO₂ and a second phase of Ta₂Zr₆O₁₇. The decreasing in final density is attributed to the increase of m-ZrO₂ content. Complete destabilization of t-ZrO₂ to m-ZrO₂ in samples added with 2.5 mol% Ta₂O₅ is interpreted by the compensation effect based on donor- and acceptor-codoping defect chemistry.     

The effect of sintering temperature on the development of grain boundary traps in zinc oxide based varistors

A series of zinc oxide based varistors containing 0.5 wt% Bi₂O₃ and 0.5 wt% Mn₂O₃ was prepared by a conventional mixed oxide route and sintered at temperatures between 950° and 1300°C. All samples showed varistor behaviour, although as the sintering temperature was increased from 950°C to 1300°C, the non-linearity coefficient, α, decreased from 22 to 3. Deep level transient spectroscopy of the varistors showed that the main active electron trap migrated to shallower levels within the bandgap as the sintering temperature increased. At the lowest sintering temperature, where α attained the highest values, a second, shallower trap was also activated.     

Transparent Lu2O3:Eu ceramics by sinter and HIP optimization

Evolution of porosity and microstructure was observed during densification of lutetium oxide ceramics doped with europium (Lu₂O₃:Eu) fabricated via vacuum sintering and hot isostatic pressing (HIP’ing). Nano-scale starting powder was uniaxially pressed and sintered under high vacuum at temperatures between 1575 and 1850 °C to obtain densities ranging between 94% and 99%, respectively. Sintered compacts were then subjected to 200 MPa argon gas at 1850 °C to reach full density. Vacuum sintering above 1650 °C led to rapid grain growth prior to densification, rendering the pores immobile. Sintering between 1600 and 1650 °C resulted in closed porosity yet a fine grain size to allow the pores to remain mobile during the subsequent HIP’ing step, resulting in a fully-dense highly transparent ceramic without the need for subsequent air anneal. Light yield performance was measured and Lu₂O₃:Eu showed ∼4 times higher light yield than commercially used scintillating glass indicating that this material has the potential to improve the performance of high energy radiography devices.     

Transparency of LiTaO3-SiO2-Al2O3 glass-ceramics in relation to their microstructure

The glasses with various compositions in the LiTaO₃-SiO₂-Al₂O₃ system were heated from room temperature to temperatures ranging from 750° to 1050° C at a rate of 5° C min^–1. From the glasses in the LiTaO₃-SiO₂ system no transparent glass-ceramic was obtained even when their LiTaO₃/SiO₂ mole ratios were as high as 2.33. The diameter and number of the LiTaO₃ crystal grains precipitated in the glasses were 5–15 m and 10⁸–10¹⁰ grains cm^–3, respectively. On the contrary, transparent glass-ceramics were obtained from the glasses containing Al₂O₃; their compositions covered a fairly large area in the LiTaO₃-SiO₂ -Al₂O₃ system, which encompasses the compositions with the LiTaO₃/SiO₂+AlO_1.5 mole ratio as low as 0.25. The diameter and number of the LiTaO₃ crystal grains precipitated in the transparent glass-ceramics were as small as 10–20 nm and as many as 10¹⁶–10¹⁸ grains cm^–3, respectively. High nucleation rates of the LiTaO₃ crystals in the Al₂O₃-containing glasses were interpreted in terms of structural inflexibility induced in the glass-network by the addition of Al₂O₃ to the LiTaO₃-SiO₂ system.     

Near zero thermal expansion properties in antiperovskite Mn3Cu0.6Ge0.4N prepared by spark plasma sintering

Antiperovskite manganese nitride Mn₃Cu_0.6Ge_0.4N was fabricated by spark plasma sintering (SPS) at different temperatures and its negative thermal expansion behavior was investigated. It is observed that the width of negative thermal expansion (NTE) operation-temperature window becomes broader when the sintering temperature decreases. Moreover, it is significantly larger than that of other Mn₃CuN-based antiperovskite manganese nitrides prepared by solid-state reaction. More interestingly, the Mn₃Cu_0.6Ge_0.4N sintered at 650 °C shows near zero thermal expansion (ZTE) behavior in the temperature range of 220–170 K. The average linear coefficient of thermal expansion (CTE) is estimated to be −0.9 × 10⁻⁶ K⁻¹. Magnetic measurement shows that the process of the magnetic transition becomes slow when the sintering temperature decreases. This antiperovskite manganese nitride Mn₃Cu_0.6Ge_0.4N with ZTE behavior is much useful for applications in the fields of cryogenics and applied superconductivity.     

Phase transformation and low temperature sintering of manganese oxide and scandia co-doped zirconia

The powders of 89 mol% ZrO₂-11 mol% Sc₂O₃ (11ScSZ) doped with various Mn₂O₃ contents were prepared by a co-precipitation method combined with a SCFD (supercritical fluid drying) route. Inhibition of the cubic-rhombohedral phase transformation in both oxidation and reduction atmospheres is achieved for 11ScSZ by the addition of 2.0 mol% Mn₂O₃. The Mn₂O₃ addition can lower the sintering temperature of 11ScSZ ceramics, and the 11ScSZ-2Mn₂O₃ compact can be sintered to nearly full density at 850 °C. 11ScSZ-2Mn₂O₃ ceramic with the cubic structure sintered at 900 °C possesses the conductivity of ∼ 0.10 S cm^− 1 at 800 °C, which is very promising for intermediate temperature solid oxide fuel cell (SOFC) applications.     

Sintering and characterization of Al2O3-B4C composites

The effect of B₄C on the densification, microstructure and mechanical properties of pressureless sintered Al₂O₃-B₄C composites have been studied. Sintering was performed without sintering additives with varying B₄C content from 0–40 vol %. Up to 20 vol % B₄C, more than 97% theoretical density was always obtained when sintered at 1850 °C for 60 min. On increasing the sintering time from 30–120 min, there was no change in density. The result of X-ray diffraction analysis showed that no reaction occurred between Al₂O₃ and B₄C. The grain growth of Al₂O₃ was inhibited by B₄C particles pinned at the grain boundary and the grain-boundary drag effect. The critical amount of B₄C to drag the grain boundary migration effectively was believed to occur at 10 vol % B₄C sintered at 1850 °C for 60 min. The maximum three-point flexural strength was found to be 550 MPa for the specimen containing 20 vol % B₄C, and the maximum microhardness was 2100 kg mm^–2 for 30 vol % B₄C specimen.     

Synthesis of BaTi4O9 ceramics by reaction-sintering process

Synthesis of BaTi₄O₉ ceramics by a reaction-sintering process was investigated. The mixture of raw materials for stoichiometric BaTi₄O₉ were pressed and sintered into ceramics without any calcination stage involved. Pure BaTi₄O₉ phases were obtained at 1150-1280 °C. High-sintered density, 98.2-99.5% of theoretical value (4.533 g/cm³), can be obtained for pellets sintered at 1200-1280 °C for 2-6 h. Some rod-shaped grains 3-7 μm in the longitudinal axis appear in pellets sintered at 1230 °C. Both the size and the amount of these rod-shaped grains increase at higher sintering temperature.     

Properties of NbC-Co cermets obtained by spark plasma sintering

Sub-micrometer sized NbC-Co powder mixtures with 8, 12, 18 or 24.5 wt.% Co were consolidated by spark plasma sintering (SPS) for 2 min at 1200-1280 °C and 30-60 MPa. The optimum densification conditions were determined by analysing the dimensional change of the NbC-12 wt.% Co powder compact. SPS for 2 min at 1280 °C under a pressure of 60 MPa allowed full densification of the NbC-Co cermets with limited NbC grain growth. The microstructure is characterized as a highly interconnected NbC grain network with an inhomogeneously distributed Co binder. The Vickers hardness increased from 11.70 to 15.40 GPa whereas the fracture toughness decreased from 9.0 to 5.5 MPa m^1 / 2 with decreasing Co content from 24.5 to 8 wt.%.     

Sintering and electromagnetic properties of BaFe12O19 ferrite prepared by co-precipitation method

BaFe₁₂O₁₉ (BaM) was synthesized through the co-precipitation route. Pure phase BaM was formed after calcination of precipitated powder at 900 °C. BaM was sintered at three different temperatures; 1100, 1200, and 1300 °C to study the sintering kinetics by varying the sintering time from 1 to 4 h. Apparent porosity decreased, and bulk density increased with increasing sintering temperature and period. A bulk density of about 4.6 g/cm³ was achieved after sintering at 1300 °C/4 h. The rate-controlling mechanism of BaM densification was the diffusion of oxygen, and the activation energy for the sintering process was 274 kJ/mol. The grain size of BaM increased with rising sintering temperatures. Permittivity increased from about 11 to 17 and the permeability increased from about 10 to 16 with the increase in sintering temperature from 1100 to 1300 °C. Saturation magnetization was also enhanced to about 69 emu/g after sintering at 1300 °C/4 h. Therefore, BaM ferrite synthesized through the co-precipitation route can be effectively used for high-frequency applications after sintering at 1300 °C.