Study of air oxidation of amorphous Zr<Subscript>65</Subscript>Cu<Subscript>17.5</Subscript>Ni<Subscript>10</Subscript>Al<Subscript>7.5</Subscript> by X-ray photoelectron spectroscopy (XPS)

The oxidation of the bulk amorphous alloy Zr₆₅Cu_17.5Ni₁₀Al_7.5 in air in its amorphous and the supercooled liquid states was studied in the temperature range 573–663 K using X-ray photoelectron spectroscopy (XPS). The oxide film mainly consisted of the oxides of Zr (as ZrO₂) and Al (as Al₂O₃). No Cu or Ni was found in the oxide film formed on the amorphous state of the alloy while significant Cu (as CuO) was present in the oxide film formed on the alloy in its supercooled liquid state. The role of the various alloying elements during oxidation at high temperatures in air is discussed in the paper. The XPS data from oxide film support the previously suggested mechanism for oxidation of this alloy, i.e. the rate controlling process during oxidation of the alloy at low temperatures (in the amorphous state) is the back-diffusion of Ni and Cu, while the oxidation at high temperatures (in the supercooled liquid state) is dominated by the inward diffusion of oxygen.     

Synthesis and variable temperature electrical conductivity studies of highly ordered TiO<Subscript>2</Subscript> nanotubes

Rafts of aligned, high aspect ratio TiO₂ nanotubes were fabricated by an electrochemical anodization method and their axial electrical conductivities were determined over the temperature range 225–400 °C. Length, outer diameter, and wall thickness of the nanotubes were approximately 60–80 μm, 160 nm, and 30 nm, respectively. Transmission electron microscopy studies confirmed that the TiO₂ nanotubes were initially amorphous, and became polycrystalline anatase after heat treatment at temperatures as low as 250 °C in air. The activation energy for conductivity over the temperature range 250–350 °C was found to be 0.87 eV. The conductivity values are comparable to those of nanocrystalline and nanoporous anatase thin films reported in literature.     

Low temperature preparation of the Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript> ceramics with the addition of BaO and B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The Zn₂SiO₄ ceramics with the addition of BaO and B₂O₃ are fabricated by traditional solid-state preparation process at a sintering temperature of 900 °C. The introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is achieved by adding 10 and 20 wt. % flux BB to the mixed ZnO-SiO₂ ceramic powders pre-sintered at 1,100 °C, respectively. The chemical composition of the flux BB (50 wt.%BaO-50 wt.% B₂O₃) is located at a liquid phase zone with a temperature range of about 869–900 °C in the binary diagram BaO-B₂O₃. In addition, the introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is also achieved by the means of a chemical combination of H₂SiO₃, H₃BO₃, ZnO and Ba(OH)₂·8H₂O, which can result in the formation of the hydrated barium borates with low melting characteristics. In turn, by the liquid sintering aid of the barium borate melts, the preparation process of the Zn₂SiO₄ ceramics can be further simplified. In the two preparation methods, the Zn₂SiO₄ ceramics with the 1.5–2.0 ZnO/SiO₂ molar ratios and the addition of a 10 wt. % flux BB can show good dielectric properties whereas the bending strength mainly depends on the microstructure of the Zn₂SiO₄ ceramics and SiO₂ content in the composition of the specimen.     

Sintering and electrical properties of Ce<Subscript>0.8</Subscript>Sm<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> film prepared by spray pyrolysis and tape casting

Ce_0.8Sm_0.2O_1.9 (SDC) powder was synthesized by spray pyrolysis at 650 °C. XRD results showed that phase-pure SDC powder with an average crystallite size of 11 nm was synthesized. SDC electrolyte film was prepared by tape casting and sintered at different temperatures of 1,300, 1,400 and 1,500 °C for 2 h, respectively. The SDC electrolyte film was relatively denser and showed finer microstructure at relatively lower temperature of 1,400 °C, which might be due to the high sintering activity of the spray pyrolysis SDC powder. The ionic conductivity of the SDC electrolyte film sintered at 1,400 °C reached a maximum value of 9.5 × 10⁻³ S cm⁻¹ (tested at 600 °C) with an activation energy for conduction of 0.90 eV.     

High-temperature oxidation behaviour of Ti<Subscript>3</Subscript>Si<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>C<Subscript>2</Subscript> in air

The oxidation behaviours of bulk Ti₃Si_(1−x)Al _x C₂ prepared by hot pressing were investigated. The results showed that the isothermal oxidation behaviour of Ti₃SiC₂ obeyed a parabolic law between 900 and 1100°C, and followed a two-step parabolic rate law between 1200°C and 1300°C. The cyclic oxidation behaviour of material is assumed to obey a three-step parabolic rate law at 1100°C and 1200°C. The calculated activation energy of isothermal oxidation is 101·43 kJ·mol⁻¹. The oxide layers consisted of a mass of α-Al₂O₃ and little TiO₂ and SiO₂ are observed on Ti₃SiC₂ as a dense and adhesive protect scale. The oxidation mechanism varies with the additive aluminum that greatly improves the oxidation resistance of Ti₃SiC₂.     

Varistor properties and aging behavior of ZnO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> ceramics with sintering process

The microstructure, electrical properties, and DC-accelerated aging behavior of the ZnO-V₂O₅-Mn₃O₄ ceramics were investigated at different sintering temperatures of 850–925°C. The microstructure of the ZnO-V₂O₅-Mn₃O₄ ceramics consisted of ZnO grain as a primary phase, and Zn₃(VO₄)₂ which acts as a liquid-phase sintering aid, in addition to Mn-rich phase as secondary phases. The maximum value (3,172 V/cm) and minimum value (977 V/cm) of breakdown field were obtained at sintering temperature of 850 and 900°C, respectively. The nonlinear coefficient exhibited the highest value, reaching 30 at 925°C and the lowest value, reaching 4 at 850°C. The optimum sintering temperature was 900°C, which exhibited not only high nonlinearity with 24 in nonlinear coefficient, but also the high stability, with %ΔE_1mA = −0.9% and %∆α = −12.5% for DC-accelerated aging stress of 0.85 E_1mA/85°C/24 h.     

The Development of Microstructure and Ferroelectric Properties of Bi<Subscript>4</Subscript>Ti<Subscript>3.96</Subscript>Nb<Subscript>0.04</Subscript>O<Subscript>12</Subscript> Thin Films

Bi₄Ti_3.96Nb_0.04O₁₂ thin films were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel method and rapid thermal annealing. The effects of Nb-substitution and annealing temperature (500–800°C) on the microstructure and ferroelectric properties of bismuth titanate thin films were investigated. X-ray diffraction analysis reveals that the intensities of (117) peaks are relatively broad and weak at annealing temperatures smaller than 700°C. With the increase of annealing temperature from 500°C to 800°C, the grain size of Bi₄Ti_3.96Nb_0.04O₁₂ thin films increases. The Bi₄Ti_3.96Nb_0.04O₁₂ thin films annealed at 700°C exhibit the highest remanent polarization (2P _r), 36 μC/cm² and lowest coercive field (2E _c), 110 kV/cm. The improved ferroelectric properties can be attributed to the substitution of Nb⁵⁺ to Ti⁴⁺ in Bi₄Ti₃O₁₂ assisting the elimination of defects such as oxygen vacancy and vacancy complexes.     

Electrical conduction properties of Sr-doped Bi<Subscript>4</Subscript>(SiO<Subscript>4</Subscript>)<Subscript>3</Subscript> with the eulytite-type structure

Electrical conduction in 1 mol% Sr-doped Bi₄(SiO₄)₃ with the eulytite-type structure at elevated temperatures was investigated with conductivity measurements. Conductivity of the material under wet condition was higher than that under dry condition, and were 1.2 × 10⁻⁶ – 9.7 × 10⁻⁵ S cm⁻¹ at 500–850 ^°C. From H/D isotope effects and p(O₂)-dependencies of the conductivity, it was found that the Sr-doped Bi₄(SiO₄)₃ exhibited protonic conduction at all the temperatures investigated while contribution of p-type conduction became significant with increasing p(O₂) and/or temperature. Protonic and p-type conductions in the material were discussed in terms of defect equilibria.     

XPS study of the initial oxidation of the bulk metallic glass Zr<Subscript>46.75</Subscript>Ti<Subscript>8.25</Subscript>Cu<Subscript>7.5</Subscript>Ni<Subscript>10</Subscript>Be<Subscript>27.5</Subscript>

The surface oxidation behaviour of the bulk metallic glass Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 was investigated in situ by using X-ray photoelectron spectroscopy (XPS). The initial stages of oxidation at room temperature were studied by exposing the clean alloy specimen surface to varying doses of pure oxygen (up to 1,000 L) in an UHV chamber. Progressive oxidation of Zr, Be and Ti was observed with increasing doses, the major species in the oxide layer being Zr(IV) and Be(II) possibly existing as ZrO₂, BeO, while Cu and Ni remained in their elemental forms. High temperature in situ oxidation in the temperature range 423–653 K for a fixed oxygen dose of 300 L was also investigated. Oxidation of Be was observed at all temperatures, while a sharp decrease in the oxidation of Zr and Ti was observed for temperatures at 573 K and above. The results show a preferential oxidation of Be and Zr at room temperature, while at higher temperatures oxidation is controlled by the reduction of oxides of Zr and Ti and the diffusion of oxygen into the alloy bulk. The role of the dissolved carbon impurity in the reduction of the oxides is discussed.     

Preparation and mechanical properties of ZrB<Subscript>2</Subscript>-based ceramics using MoSi<Subscript>2</Subscript> as sintering aids

ZrB₂ (zirconium diboride)-based ceramics reinforced by 15vol.% SiC whiskers with high density were successfully prepared using MoSi₂ as sintering aids. The effects of sintering condition and MoSi₂ content on densification behavior, phase composition, and mechanical properties of SiC_w/ZrB₂ composites were studied. Nearly, fully dense materials (relative density >99%) were obtained by hot-pressing (HP) at 1700°C–1800°C in flow argon atmosphere. The grain size of ZrB₂ phase in the samples sintered by HP at 1700°C–1800°C were very fine, with mean size below 5 μm. Mechanical properties (such as flexural strength, fracture toughness, and Vickers hardness) of the sintered samples were measured. The sample with 15vol.% MoSi₂ addition sintered by HP at 1750°C displayed the best mechanical properties.     

Low-temperature sintering of SiC reticulated porous ceramics with MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> additives as sintering aids

SiC reticulated porous ceramics (SiC RPCs) was fabricated with polymer replicas method by using MgO–Al₂O₃–SiO₂ additives as sintering aids at 1,000∼1,450 °C. The MgO–Al₂O₃–SiO₂ additives were from alumina, kaolin and Talc powders. By employing various experimental techniques, zeta potential, viscosity and rheological measurements, the dispersion of mixed powders (SiC, Al₂O₃, talc and kaolin) in aqueous media using silica sol as a binder was studied. The pH value of the optimum dispersion was found to be around pH 10 for the mixtures. The optimum condition of the slurry suitable for impregnating the polymeric sponge was obtained. At the same time, the influence of the sintering temperature and holding time on the properties of SiC RPCs was investigated. According to the properties of SiC RPCs, the optimal sintering temperature was chosen at 1,300 °C, which was lower than that with Al₂O₃–SiO₂ additives as sintering aids.     

Microwave dielectric properties and its compatibility with silver electrode of LiNb<Subscript>0.6</Subscript>Ti<Subscript>0.5</Subscript>O<Subscript>3</Subscript> with B<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO additions

The influences of B₂O₃ and CuO (BCu, B₂O₃: CuO = 1:1) additions on the sintering behavior and microwave dielectric properties of LiNb_0.6Ti_0.5O₃ (LNT) ceramics were investigated. LNT ceramics were prepared with conventional solid-state method and sintered at temperatures about 1,100 °C. The sintering temperature of LNT ceramics with BCu addition could be effectively reduced to 900 °C due to the liquid phase effects resulting from the additives. The addition of BCu does not induce much degradation in the microwave dielectric properties. Typically, the excellent microwave dielectric properties of ε_r = 66, Q × f = 6,210 GHz, and τ _f  = 25 ppm/^oC were obtained for the 2 wt% BCu-doped sample sintered at 900 °C. Chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Pyrolysis of aluminium loaded polymethylsiloxanes: the influence of Al/PMS ratio on mullite formation

Al-filler-loaded polymethylsiloxane (PMS) was pyrolysed in air atmosphere at temperatures 400–1700 °C. The effect of the Al amount added to the PMS on phase development, densification behaviour and microstructure evolution was studied by simultaneous thermal analysis, X-ray diffraction, scanning electron microscopy and electron probe microanalysis. The Al/PMS reaction route is complex producing Si, SiO₂ (amorphous and cristobalite), Al₂O₃ (γ-, ι- and α-Al₂O₃), Al₂OC, Al₄O₄C, Al₄SiC₄, and AlN, depending on the ratio of Al/PMS in the initial mixture. Increasing the Al content (high Al/PMS ratio) reduces the amount of voids and porosities after PMS degradation. The voids and porosities provide access for the oxygen atmosphere into the inner structure to oxidise the Al particles, Si or SiC and also as channels for the PMS degradation products to escape. Mullite formation was identified in sample containing >73 wt% Al at temperature as low as 1400 °C.     

Preparation of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> · 6SrB<Subscript>2</Subscript>O<Subscript>4</Subscript> magnetic composites by spray pyrolysis

Spray pyrolysis has been used to produce X-ray amorphous precursors with the nominal composition SrFe₁₂O₁₉ · 6SrB₂O₄ in the form of spherical particles 0.3 to 2 μm in diameter. Heat treatment of the precursors at temperatures from 650 to 900°C has produced platelike strontium hexaferrite particles embedded in a SrB₂O₄ matrix. With increasing annealing temperature, the average dimensions of the hexaferrite particles increase from 80 × 20 to 450 × 100 nm and the coercivity of the material rises from 240 to 440 kA/m.     

Low-temperature synthesis of Sr<Subscript>0.3</Subscript>Ba<Subscript>0.7</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> ultrafine powder and its characteristics

Ultrafine strontium barium niobate (Sr_0.3Ba_0.7Nb₂O₆, SBN30) powders were prepared by urea method starting from a precursor solution constituting of Sr (NO₃)₂, Ba (NO₃)₂, NbF₅, urea and polyvinyl alcohol (PVA) as surfactant. Their structural behavior and morphology were examined by means of X-ray diffractometry (XRD) and Scanning electron microscopy (SEM). The results showed that the SBN30 powders crystallized to a pure tetragonal phase at annealing temperatures as low as 750 °C. The average particle size of SBN powders subjected to 750 °C was of the order of 150–300 nm. With increasing calcination temperature,however, the average particle size of the calcined powders increased. The SBN30 ceramic prepared from urea method can be sintered at temperature as low as 1,225 °C. The transition temperature from the ferroelectric phase to the paraelectric phase and the relative dielectric permittivity of the SBN30 powder were less than the corresponding values of the bulk ceramic. The permittivity and loss tangent (tan δ) at room temperature (1 kHz) was found to be 930 and below 0.025.     

Microstructure and electrical properties of Pr<Subscript>6</Subscript>O<Subscript>11</Subscript> doped ZnO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-based varistors

The microstructure and electrical properties of ZnO-Bi₂O₃-based varistor ceramics doped by Pr₆O₁₁ in the content range of 0–5.49 wt% were investigated at different sintering temperatures (1,100, 1,150, 1,175, 1,200 °C). The increase of sintering temperature leads to more dense ceramics, which increases the nonlinear property, whereas it decreases the voltage-gradient and leakage current. With increasing Pr₆O₁₁ content, the breakdown voltage increases because of the decreases of ZnO grain size. The improvement of non linear coefficient together with the decrease of leakage current are related to the uniformly distribution of secondary phases along the grain boundaries of the ZnO. The varistors sintered at 1,175 °C with the 3.37 wt% Pr₆O₁₁ doping possess the best electrical properties: the varistor voltage, nonlinear coefficient, and leakage current are 340 V/mm, 46 and 0.63 μA, respectively.     

Ion conduction in vanadium-substituted LiSn<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript> electrolyte nanomaterials

LiSn₂P_3 − y V _y O₁₂ powders with y = 0.2, 0.4, 0.6, and 0.8 are prepared by mechanochemical milling method. The pellets of the compounds are heat treated at temperatures between 700 to 1,000 °C for sintering period of 8 h. X-ray diffraction analysis indicates that all samples consist of rhombohedral crystalline LiSn₂P₃O₁₂ phase. Energy dispersive X-ray analysis confirmed that V⁵⁺ has been successfully substituted into LiSn₂P₃O₁₂ crystalline phase. The conductivities of the pellets are determined using impedance spectroscopy. Impedance analysis shows enhancement in both bulk and grain boundary conductivities with increase in y. The enhancement in bulk conductivity is due to decrease in bulk activation energy reflecting an increase in ion mobility as a result of an increase in bottleneck size. Enhancement in grain boundary conductivity is attributed to increase in the number of conducting pathways due to an increase in crystallite homogeneity.     

Study of the structural and dielectric properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> and PbO addition on BiNbO<Subscript>4</Subscript> ceramic matrix for RF applications

In this paper, the structural and dielectric properties of BNO (BiNbO₄) was investigated as a function of the external RF frequency and temperature. The BNO Ceramics, prepared by the conventional mixed oxide method and doped with 3, 5 and 10 wt. % Bi₂O₃–PbO were sintered at 1,025 °C for 3 h. The X-ray diffraction patterns of the samples sintered, shown the presence of the triclinic phase (β-BNO). In the measurements obtained at room temperature (25 °C) was observed that the largest values of dielectric permittivity (ε′ _r ) at frequency 100 kHz, were for the samples: BNO5Bi (5 wt. % Bi₂O₃) and BNO5Pb (5 wt. % PbO) with values ε′ _r ~ 59.54 and ε′ _r ~ 78.44, respectively. The smaller values of loss tangent (tan δ) were for the samples: BNO5Bi and BNO3Pb (3 wt. % PbO) with values tan δ ~ 5.71 × 10⁻⁴ and tan δ ~ 2.19 × 10⁻⁴, respectively at frequency 33.69 MHz. The analysis as a function of temperature of the dielectric properties of the samples, obtained at frequency 100 kHz, showed that the larger value of the relative dielectric permittivity was about ε′ _r ~ 76.4 at temperature 200 °C for BNO5Pb sample, and the value smaller observed of dielectric loss was for BNO3Bi sample at temperature 80 °C, with about tan δ ~ 5.4 × 10⁻³. The Temperature Coefficient of Capacitance (TCC) values at 1 MHz frequency, present a change of the signal from BNO (−55.06 ppm/°C) to the sample doped of Bi: BNO3Bi (+86.74 ppm/°C) and to the sample doped of Pb: BNO3Pb (+208.87 ppm/°C). One can conclude that starting from the BNO one can increase the doping level of Bi or Pb and find a concentration where one have TCC = 0 ppm/°C, which is important for temperature stable materials applications like high frequency capacitors. The activation energy (H) obtained in the process is approximately 0.55 eV for BNO sample and increase with the doping level. These samples will be studied seeking the development ceramic capacitors for applications in radio frequency devices.     

Low-firing Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> microwave dielectric ceramics with BaCu(B<Subscript>2</Subscript>O<Subscript>5</Subscript>) additive

Phase purity, microstructure, sinterability and microwave dielectric properties of BaCu(B₂O₅)-added Li₂ZnTi₃O₈ ceramics and their cofireability with Ag electrode were investigated. A small amount of BaCu (B₂O₅) can effectively reduce the sintering temperature from 1075°C to 925°C, and it does not induce much degradation of the microwave dielectric properties. Microwave dielectric properties of ε _r = 23·1, Q × f = 22,732 GHz and τ _f = − 17·6 ppm/°C were obtained for Li₂ZnTi₃O₈ ceramic with 1·5 wt% BaCu(B₂O₅) sintered at 925°C for 4 h. The Li₂ZnTi₃O₈ +BCB ceramics can be compatible with Ag electrode, which makes it a promising microwave dielectric material for low-temperature co-fired ceramic technology application.     

Mechanical properties of bovine hydroxyapatite (BHA) composites doped with SiO<Subscript>2</Subscript>, MgO,Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and ZrO<Subscript>2</Subscript>

Biologically derived hydroxyapatite from calcinated (at 850 °C) bovine bones (BHA) was doped with 5 wt% and 10 wt% of SiO₂, MgO, Al₂O₃ and ZrO₂ (stabilized with 8% Y₂O₃). The aim was to improve the sintering ability and the mechanical properties (compression strength and hardness) of the resultant BHA-composites. Cylindrical samples were sintered at several temperatures between 1,000 and 1,300 °C for 4 h in air. The experimental results showed that sintering generally occurs at 1,200 °C. The BHA–MgO composites showed the best sintering performance. In the BHA–SiO₂ composites, extended formation of glassy phase occurred at 1,300 °C, resulting in structural degradation of the resultant samples. No sound reinforcement was achieved in the case of doping with Al₂O₃ and zirconia probably due to the big gap between the optimum sintering temperatures of BHA and these two oxides.